WO2018194414A1 - Printed circuit nanofiber web manufacturing method, printed circuit nanofiber web manufactured thereby, and electronic device employing same - Google Patents

Printed circuit nanofiber web manufacturing method, printed circuit nanofiber web manufactured thereby, and electronic device employing same Download PDF

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Publication number
WO2018194414A1
WO2018194414A1 PCT/KR2018/004600 KR2018004600W WO2018194414A1 WO 2018194414 A1 WO2018194414 A1 WO 2018194414A1 KR 2018004600 W KR2018004600 W KR 2018004600W WO 2018194414 A1 WO2018194414 A1 WO 2018194414A1
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WO
WIPO (PCT)
Prior art keywords
nanofiber web
printed circuit
nanofiber
circuit pattern
manufacturing
Prior art date
Application number
PCT/KR2018/004600
Other languages
French (fr)
Korean (ko)
Inventor
서인용
Original Assignee
주식회사 아모그린텍
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170051596A external-priority patent/KR20180118374A/en
Application filed by 주식회사 아모그린텍 filed Critical 주식회사 아모그린텍
Priority to US16/606,192 priority Critical patent/US11324123B2/en
Priority to CN201880025889.5A priority patent/CN110537394B/en
Publication of WO2018194414A1 publication Critical patent/WO2018194414A1/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0277—Bendability or stretchability details
    • H05K1/0283—Stretchable printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H05K1/118—Printed elements for providing electric connections to or between printed circuits specially for flexible printed circuits, e.g. using folded portions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/06—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1605—Process or apparatus coating on selected surface areas by masking
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1644—Composition of the substrate porous substrates
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10151—Sensor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0709—Catalytic ink or adhesive for electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1173—Differences in wettability, e.g. hydrophilic or hydrophobic areas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
    • H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a printed circuit nanofiber web, and more particularly, to a method for manufacturing a printed circuit nanofiber web having flexibility, resilience, waterproofness, and breathability, and a printed circuit nanoweb manufactured through the same and an electronic device using the same. will be.
  • PCB printed circuit board
  • a general printed circuit board is a flexible printed circuit in which copper foil is adhered on a rigid printed circuit board (rigid PCB) and a polyimide substrate, in which a reinforcement such as glass fiber is added to an epoxy resin and the copper foil is bonded.
  • Flexible Printed Circuit Board (FPCB) and Rigid-Flexible Printed Circuit Board (RF PCB) which combines the advantages of a rigid printed circuit board and a flexible printed circuit board.
  • Patent Document 1 includes a step of forming a circuit pattern on a seed layer formed on a flexible insulating substrate; Applying a first photosensitive material on the circuit pattern; Exposing and developing the first photosensitive material to form a protective pattern on the circuit pattern; Etching the seed layer; And a five step of peeling the protective pattern, wherein the first photosensitive material is a liquid or film type photosensitive agent.
  • the base member is a flexible insulating substrate such as polyimide film, it does not have sufficient flexibility, it is folded or folded after being unfolded Restoration characteristics are also not expected, and there is a drawback that it is not applicable to smart devices that do not have breathability and require wearables.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a method of manufacturing a printed circuit board having flexibility and resilience by printing a circuit pattern on a nanofiber web and an electronic device using the same.
  • the present invention provides a method of manufacturing a printed circuit board using an electroless plating method which can improve the compactness and thickness uniformity of the circuit pattern portion and plate the circuit pattern portion on a flexible substrate such as a nanofiber web, and an electronic device using the same.
  • a flexible substrate such as a nanofiber web
  • the present invention by applying a nanofiber web having a plurality of pores formed by the accumulation of nano-sized fibers as the base substrate of the printed circuit board printed circuit that satisfies the flexibility, resilience and breathability required for bio patch or medical sensor
  • Another object of the present invention is to provide a method of manufacturing a substrate and an electronic device using the same.
  • the present invention comprises the steps of (1) preparing a nanofiber web by electrospinning a spinning solution containing a fiber forming component; And (2) forming a circuit pattern portion to cover an outer surface of the nanofibers included in a predetermined region on the nanofiber web by an electroless plating method.
  • the nanofiber web may have a thickness of 5 to 200 ⁇ m.
  • the nanofiber web may have a porosity of 10 to 80%.
  • the thickness of the circuit pattern portion coated on the nanofibers may be 0.1 ⁇ 10 ⁇ m.
  • the nanofiber web may have a thickness of 10 to 150 ⁇ m and porosity of 30 to 60%, the thickness of the circuit pattern portion coated on the nanofiber may be 0.1 to 3 ⁇ m.
  • step (2) 2-1) immersing the nanofiber web in a catalyst solution to catalyze the treatment; 2-2) activating the catalyzed nanofiber web; And 2-3) forming the circuit pattern part by electroless plating the activated nanofiber web.
  • the step of degreasing or hydrophilizing the nanofiber web may further include.
  • the catalyst solution may include any one or more compounds selected from the group consisting of salts of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
  • step 2-2) may be a step of activating by immersing in sulfuric acid solution.
  • the electroless plating method according to step (2) may be a step of immersing in the plating solution by masking the remaining surface except for the portion where the circuit pattern portion is to be formed on the nanofiber web.
  • the plating solution may include a metal selected from the group consisting of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
  • the printed circuit nanofiber web may include a first pattern of the upper region and a second pattern of the lower region formed by the circuit pattern portion, respectively, wherein the first pattern and the second pattern are formed in the same pattern Can be.
  • the circuit pattern portion may include a first circuit pattern portion formed on the upper surface of the nanofiber web and a second circuit pattern portion formed on the lower surface, wherein the first circuit pattern portion and the second circuit pattern portion are the same circuit It can be formed in a pattern.
  • the printed circuit nanofiber web may further include a strength reinforcing supporter on a surface facing the one surface of the nanofiber web printed circuit pattern portion.
  • the fiber forming component is polyurethane (polyurethane), polystyrene (polystylene), polyvinyl alcohol (polyvinylalchol), polymethyl methacrylate (polymethyl methacrylate), polylactic acid (polylactic acid), polyethylene oxide (polyethyleneoxide), polyvinyl Acetate (polyvinyl acetate), polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl chloride, polycarbonate, At least one member selected from the group consisting of polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate and fluorine-based compounds It may include a compound.
  • the present invention also provides a nanofiber web comprising a plurality of nanofibers; And a circuit pattern portion formed by covering an outer surface of the nanofibers included in a predetermined region on the nanofiber web.
  • the present invention is the printed circuit nanofiber web; And at least one electronic component mounted on the printed circuit nanofiber web.
  • a printed circuit nanofiber web having a printed circuit pattern having flexibility and resilience can be implemented to be suitable for future smart devices.
  • the circuit pattern portion can be formed on the flexible nanofiber web to have a dense and uniform thickness, and at the same time, the biopatch is satisfied by satisfying the waterproof and breathable characteristics through the nanofiber web having a plurality of pores. It can be applied in various future industries, including electronic devices such as medical devices, smart devices, and the like.
  • FIG. 2 is a flowchart showing an electroless plating method according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram showing a circuit pattern formed on a predetermined region of the nanofiber web according to an embodiment of the present invention
  • FIG. 4 is a perspective view showing a cross section of the nanofiber along the X-X 'boundary line shown in FIG.
  • FIGS. 7A and 7B show the thickest coating of the thickness of the circuit pattern portion plated on the nanofibers
  • FIG 8 and 9 are views showing a printed circuit nanofiber web manufactured by the manufacturing method according to an embodiment of the present invention.
  • the method of manufacturing a printed circuit nanofiber web comprises the steps of: (1) preparing a nanofiber web by electrospinning a spinning solution containing a fiber forming component; And (2) forming a circuit pattern portion to cover the outer surface of the nanofibers included in the predetermined region on the nanofiber web by electroless plating.
  • Step (1) is a step of producing a nanofiber web having a circuit pattern portion by electrospinning the spinning solution containing the fiber forming component.
  • step (1) Prior to describing step (1) according to the manufacturing method of the present invention, the reason for using the nanofiber web as a substrate for forming the circuit pattern portion will be described first.
  • a general printed circuit board is a flexible printed circuit in which copper foil is adhered on a rigid printed circuit board (rigid PCB) and a polyimide substrate, in which a reinforcement such as glass fiber is added to an epoxy resin and the copper foil is bonded. It can be divided into a flexible printed circuit board (FPCB) and a rigid-flexible printed circuit board (RF PCB) that combines the advantages of a flexible printed circuit board and a flexible printed circuit board. In particular, in the case of printed circuit boards for future devices such as smart devices reflecting the recent trend, excellent flexibility is required, and resilience and high bending characteristics that can maintain the original flat state even when folded or wrinkled are required.
  • FPCB flexible printed circuit board
  • RF PCB rigid-flexible printed circuit board
  • the polyimide used in the conventional flexible printed circuit board has a certain level of flexibility, but when folded or creased, the polyimide has a very low resilience to return to its original flat state, and is vulnerable to warpage, thus making it difficult for future devices. Is somewhat inadequate.
  • the present invention provides a printed circuit having excellent flexibility and resilience and excellent bending characteristics to be suitable for the future smart devices through a manufacturing method of printing a circuit pattern on a nanofiber web in which a plurality of nanofibers are randomly accumulated. Implement nanofiber web.
  • the printed circuit nanofiber web implemented by the manufacturing method according to the present invention forms a circuit pattern portion to surround the outer surface of the nanofibers constituting the nanofiber web, as shown in the flow chart shown in Figure 2,
  • the excellent flexibility can be fully utilized, and the recovery property of being restored after being folded or wrinkled due to the randomly stacked nanofibers can be improved.
  • the sheet of the web structure is implemented, it is possible to improve the utilization as a future-oriented device such as ultrathin devices or wearable devices.
  • the nanofiber web may be used without limitation in the case of a method of forming a fibrous web having a three-dimensional network shape by providing a nanofiber.
  • the nanofiber web may form a nanofiber web by electrospinning a spinning solution containing a fiber forming component.
  • the fiber forming component included in the spinning solution for manufacturing the nanofiber web can be used without limitation as long as it is a fiber forming component that can be commonly used in the art, preferably polyurethane, polystyrene, poly Polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethyleneoxide, polyvinyl acetate, polyacrylic acid, polycaprolactone , Polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyetherimide, polyethersulphone, polybenzimidazole polybenzimidazol), polyethylene terephthalate, polybutylene terephthalate It may comprise at least one compound selected from the group consisting of (polybutylene terephthalate), and fluorine-based compound.
  • the fluorine-based compound is polytetrafluoroethylene (PTFE) -based, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) -based, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) -based, Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE) system, tetrafluoroethylene-ethylene copolymer (ETFE) system, polychlorotrifluoroethylene (PCTFE) system, chlorotrifluoro It may include one or more compounds selected from the group consisting of a low ethylene-ethylene copolymer (ECTFE) system and a polyvinylidene fluoride (PVDF) system, preferably may include a polyvinylidene fluoride (PVDF). .
  • ECTFE low ethylene-ethylene copolymer
  • PVDF poly
  • the weight average molecular weight of the PVDF may be 10,000 to 1,000,000, preferably 300,000 to 600,000, but is not limited thereto.
  • the fiber forming component may be included in 5 to 30% by weight, preferably 8 to 20% by weight in the spinning solution. If the fiber-forming component is less than 5% by weight, it is difficult to form a fiber, and when spun, it is not spun into fiber, but even when spun and spun in a droplet, beads are formed and volatilization of the solvent does not occur so that pores are blocked. Symptoms may occur. In addition, if the fiber-forming component is more than 30% by weight, the viscosity rises and solidification occurs at the surface of the solution, which makes it difficult to spin for a long time, and the fiber diameter may increase, making it impossible to form a fibrous size of micrometer or less.
  • the spinning solution may further include a solvent
  • the solvent may be used without limitation in the case of a solvent that does not produce a precipitate of the fiber-forming component and does not affect the radioactivity of the nanofibers described later, preferably ⁇ Any one selected from the group consisting of -butyrolactone, cyclohexanone, 3-hexanone, 3-heptanone, 3-octanone, N-methylpyrrolidone, dimethylacetamide, acetone dimethyl sulfoxide, dimethylformamide It may contain the above.
  • the solvent may be a mixed solvent of dimethylacetamide and acetone.
  • the prepared spinning solution may produce nanofibers through known electrospinning devices and methods.
  • the electrospinning device uses an electrospinning device having a single spinning pack having one spinning nozzle or a plurality of single spinning packs for mass production, or an electrospinning device having a spinning pack having a plurality of nozzles. It is okay.
  • dry spinning or wet spinning having an external coagulation bath can be used, and there is no limitation according to the method.
  • a nanofiber web formed of nanofibers may be obtained when electrospinning onto a collector, for example, paper.
  • the air spray nozzle provided in the nozzle of the spinning pack may be set to the air pressure of the air injection is 0.01 ⁇ 0.2MPa range. If the air pressure is less than 0.01MPa, it does not contribute to the collection and accumulation. If the air pressure exceeds 0.2MPa, the cone of the spinning nozzle is hardened to block the needle, which may cause radiation trouble.
  • the injection rate of the spinning solution per nozzle may be 10 ⁇ 30 ⁇ m / min.
  • the distance between the tip of the nozzle and the collector may be 10 ⁇ 30cm.
  • the present invention is not limited thereto, and may be changed according to the purpose.
  • Nanofiber web prepared by performing step (1) may have a thickness of 5 ⁇ 200 ⁇ m, preferably 10 ⁇ 150 ⁇ m thickness. If the thickness of the nanofiber web is less than 5 ⁇ m the support function for the circuit pattern portion coated on the outer surface of the nanofiber provided in the nanofiber web may be reduced, the durability and mechanical properties of the printed circuit nanofiber web In addition, if the thickness of the nanofiber web exceeds 200 ⁇ m, air generated during the electroless plating process may not escape in the nanofiber web, durability and processability may be lowered, it is disadvantageous for thinning can do.
  • the nanofiber web may have a porosity of 10 to 80%, preferably 30 to 60%. If the porosity of the nanofiber web is less than 10% may reduce the elasticity, peeling phenomenon may occur when the electroless plating, durability may be reduced, if the porosity exceeds 80% printing Durability, processability and mechanical properties of the circuit nanofiber web may be degraded, and electrical properties may be degraded.
  • the printed circuit nanofiber web to be described later is opposed to one surface of the printed nanofiber web
  • the surface may further include a support for strength reinforcement.
  • it may be implemented including a first nanofiber web or a second nanofiber web laminated on one side or both sides of the strength reinforcing support, but is not limited thereto.
  • a conventional method of manufacturing a printed circuit board uses a photo-lithography process of steps (a) to (g) as shown in FIG. 1, wherein the process of forming a seed layer on the surface of the substrate using metal particles is sputtering.
  • a photo-lithography process of steps (a) to (g) as shown in FIG. 1, wherein the process of forming a seed layer on the surface of the substrate using metal particles is sputtering.
  • step (2) of the manufacturing method according to the present invention forms a circuit pattern portion to cover the outer surface of the nanofibers included in a predetermined region on the nanofiber web through the electroless plating method.
  • the electroless plating method is a technique in which a metal film is formed by spontaneous redox reaction of materials existing in a solution without applying electricity from the outside.
  • the electroless plating method is used to form a circuit pattern portion on a nanofiber web according to the present invention. It has the following advantages.
  • the uniformity of the plated circuit pattern portion can be kept constant, thereby improving electrical conductivity characteristics and reliability of electronic components using the same. That is, unlike a general photo-lithography process or electroplating method for forming a metal film, the electroless plating method precipitates metal by using a reduction reaction, so that a metal film may be uniformly formed on the surface of the substrate, thereby resulting in a product shape.
  • the uniformity as well as the stability of the electronic component can be improved.
  • the uniformity of the metal plating solution should be ensured, and an activation layer described below may be performed to prevent the occurrence of irregularities due to the formation of an oxide film.
  • the thickness of the circuit pattern portion through the electroless plating method can be easily adjusted to increase the utilization in various industries. That is, in the electroless plating method, since the material present in the plating solution uses a redox reaction on the surface of the substrate, it is possible to control the deposition rate of the reduced metal by controlling the reaction temperature and pH, thereby making the thickness of the circuit pattern portion easier. I can regulate it. When the nickel plating solution is plated through the electroless plating method according to an example, since it has the highest precipitation rate in the range of pH 4 to 6, the thickness of the circuit pattern portion may be adjusted through proper pH control.
  • the plating solution can be appropriately designed to suit the desired industrial group in consideration of the deposition rate, the life of the plating solution, and the thickness of the circuit pattern part.
  • the circuit pattern portion can be simultaneously formed on a large amount of nanofiber web through the electroless plating method, thereby achieving the effect of process simplification and cost reduction.
  • a sufficient amount of metal ions and a reducing agent are supplied, 10 to 30 times of treatment is possible compared to electroplating using the same amount of plating solution, and thus a large amount of printed circuit nanofiber web can be manufactured more quickly. It can contribute significantly to the simplification and can be environmentally friendly and cost-effective because of the reduced amount of material disposed of.
  • the electroless plating method uses a redox reaction by immersing in a plating solution, so that it is not necessary to apply a flexible substrate surface external force like a nanofiber web, and does not damage the substrate surface without special treatment. There is an advantage that can be plated.
  • a printed circuit nanofiber web according to the present invention may be performed to mask the remaining surface except for the portion where the circuit pattern portion is to be formed on the nanofiber web.
  • the masking is to form a circuit pattern portion only on a specific portion of the nanofiber web, and a known masking process for electroless plating may be used without limitation in a range that does not affect the physical properties of the nanofiber web.
  • a known masking process for electroless plating may be used without limitation in a range that does not affect the physical properties of the nanofiber web.
  • the position at which the circuit pattern portion is formed can be controlled, and in another example, a masking agent made of liquid silicon is applied by spraying. Method can be used.
  • the circuit pattern part may be formed only at a specific position through a mask manufactured in the form of a case into which the nanofiber web may be inserted. Subsequently, the masked nanofiber web may be immersed in the plating solution described below to form a circuit pattern portion only at a specific portion.
  • step (2) 2-1) immersing the nanofiber web in a catalyst solution to catalyze the treatment; 2-2) activating the catalyzed nanofiber web; And 2-3) forming the circuit pattern part by electroless plating the activated nanofiber web.
  • the step of degreasing or hydrophilizing the nanofiber web before the step (2) may further include.
  • the degreasing step is a step of washing an oxide or a foreign substance, particularly an oil or fat, present on the surface of the nanofiber web on which the circuit pattern part is to be formed by treating with an acid or an alkali surfactant.
  • an acid or an alkali surfactant used in the degreasing step are not washed thoroughly, they can act as contaminants for subsequent treatment solutions (catalyst solutions or activating solutions), so that the surfactants can You must wash.
  • the hydrophilization step converts the surface of the hydrophobic nanofiber web into hydrophilic and simultaneously introduces functional groups such as carboxyl groups, amine groups and hydroxyl groups to the nanofiber web surface to facilitate the adsorption of metal ions and fine cavities on the nanofiber web surface. It is a step of improving the adhesion between the surface of the deposited metal film and the nanofiber web by increasing the surface roughness.
  • the hydrophilization step may be performed by mixing an alkali metal hydroxide or nitrogen compound with a surfactant, the hydroxide may be used sodium hydroxide (NaOH), potassium hydroxide (KOH), etc., the nitrogen compound is an ammonium salt or an amine compound And the like.
  • the ammonium salt is, for example, ammonium salt substituted with an alkyl group or an aryl group, such as ammonium hydroxide, ammonium chloride, ammonium sulfate, ammonium carbonate or triethylammonium salt, tetraethylammonium salt, trimethylammonium salt, tetramethylammonium salt, trifluoroammonium salt or tetrafluoroammonium salt.
  • the amine compound may be, for example, aliphatic amine compounds such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, ethylenediamine, diethylenetriamine, or urea and hydrazine derivatives. Can be used.
  • the surfactant may be anionic surfactants such as sodium alkyl sulfonate (SAS), sodium sodium sulfate ester (AS), sodium olefin sulfonate (AOS), alkyl bezen sulfonate (LAS), cationic surfactants, or neutral surfactants.
  • SAS sodium alkyl sulfonate
  • AS sodium sodium sulfate ester
  • AOS sodium olefin sulfonate
  • LAS alkyl bezen sulfonate
  • cationic surfactants or neutral surfactants.
  • the catalyst particles are deposited on the surface of the nanofiber web subjected to the degreasing and hydrophilization to carry out the catalyzing treatment to facilitate plating.
  • the catalyst solution includes at least one compound selected from the group consisting of salts of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, preferably Ti, Sn, Au, It can be used as a colloidal solution consisting of salts of Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, or a noble metal complex ion.
  • the colloidal solution is at least one selected from the group consisting of 50 to 250 ml of hydrochloric acid per liter of ultrapure water, 50 to 300 g of sodium chloride or potassium chloride, 5 to 60 g of tin chloride (SnCl 2 ), and 0.1 to 5 g of palladium chloride (PdCl 2 ). Solutions containing salts can be used.
  • a pre-dip process may be performed, and the pre-deposition process is performed at a low temperature prior to the catalyst treatment. It is a treatment step for preventing the contamination of the catalyst solution used in the catalyst treatment step or the concentration change by immersing the nanofiber web in the catalyst solution of.
  • step 2-2 of activating the catalyzed nanofiber web is performed.
  • the activation step is a step for improving the activity of the adsorbed metal particles and the precipitation behavior of the electroless plating solution after the catalysis step. Through this activation step, the metal particles surrounding the colloidal particles are removed and only the adsorbed catalyst remains, thereby making the deposition of the electroless metal film even easier.
  • the activation process may be a step of depositing 30 seconds to 5 minutes, preferably 30 seconds to 3 minutes in a mixed solution of distilled water and sulfuric acid.
  • steps 2-3) are performed on the activated nanofiber web to form a circuit pattern part by electroless plating.
  • the electroless plating method may be generally divided into reduction plating method and substitution plating method, and reduction plating method is a method in which metal is precipitated and plated on the surface of a substrate through reduction reaction, and substitution plating method has a relatively large reducing power due to a difference in reducing power of metal.
  • a metal is deposited and plated, and the step 2-3) may use a substitution plating method according to an embodiment of the present invention.
  • the nanofiber web is immersed in the primary plating solution having a relatively low reducing power, and the nanofiber web is immersed in the secondary plating solution having a relatively reducing power, thereby depositing and plating the metal of the secondary plating solution.
  • the primary and secondary plating solution may include a metal selected from the group consisting of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, such substitution plating method
  • a copper ion plated printed circuit nanofibrous web can be finally obtained by immersing at 40 to 80 ° C. for 0.5 to 10 minutes, preferably at 45 to 75 ° C. for 1 minute to 8 minutes.
  • the circuit pattern part formed on the printed circuit nanofiber web through step (2) is formed by covering the outer surface of the nanofiber included in a predetermined area on the nanofiber web. That is, referring to FIGS. 3 and 4, the nanofibers in the predetermined region (region A) of the nanofiber web on which the circuit pattern portion is formed are different from the outer region of the nanofiber, unlike the region (region B) of the nanofiber web on which the circuit pattern portion is not formed. It may be made of nanofibers, such as the sheath / core form coated on the circuit pattern portion.
  • the circuit pattern portion may have a thickness of 0.1 to 10 ⁇ m, preferably 0.2 to 3 ⁇ m. If the thickness of the circuit pattern portion is less than 0.1 ⁇ m may be advantageous in thinning, but because the thickness of the circuit pattern portion is too thin, there is a fear that the stability of the electrical characteristics through the circuit pattern portion is lowered, the adhesion between the circuit pattern portion and the nanofiber web The degradation may cause problems in product durability and reliability, and as the porosity of the printed circuit nanofiber web increases, durability and mechanical properties may decrease.
  • the support function of the nanofiber web due to the weight of the circuit pattern portion may degrade the mechanical properties, may be disadvantageous in light weight and thin screen as a use of small electronic products.
  • the porosity of the printed circuit nanofiber web is lowered, there may be a problem that the elasticity is lowered, and durability and processability may be lowered.
  • the nanofiber web according to an embodiment of the present invention may include a first pattern of the upper region and a second pattern of the lower region formed by the circuit pattern portion, respectively, the first pattern and the second pattern It may be formed in the same pattern with each other.
  • the same circuit pattern can be formed through one immersion by adjusting the thickness of the nanofiber web, which has advantages in process simplification and economics.
  • the first pattern portion and the second pattern portion may be embodied in different circuit patterns, and may be appropriately selected in consideration of the purpose and use of the printed circuit nanofiber web according to the present invention. Is not particularly limited.
  • the printed circuit nanofiber web may form a circuit pattern layer on at least one surface of the nanofiber web through a printed electronic technique instead of using the electroless plating method in the step (2).
  • the circuit pattern can be printed in a two-step process, which greatly contributes to the simplification of the process, and improves the accuracy of the circuit pattern formation. Therefore, there is almost no wasted material, and the manufacturing cost can be greatly reduced.
  • the printed electronic technique may be a printed electronic technique commonly used in the art, and preferably, may be performed by any one method of inkjet printing and flexography.
  • the printed electronic technique in the present invention is not limited to the above-mentioned method, and may include all methods that may be used as the printed electronic technique.
  • the inkjet printing method is a method of forming a circuit pattern by ejecting conductive ink droplets (hereinafter, referred to as droplets) having a small size from a head and colliding with a target substrate, and continuously according to the droplet ejection method. It may be classified into a continuous method of discharging droplets and a drop on demand method of discharging droplets. In this case, the continuous method generally requires a large device and is used for low resolution patterning, whereas the drop on demand method is used when high resolution patterning is required.
  • the Drop On Demand method uses a piezo method that applies pressure to ink again using a piezoelectric element and heats the ink to generate air bubbles and then to the pressure of the bubbles. Can be classified into a bubble jet method for discharging droplets.
  • the Piezo method it is advantageous that the head life is relatively long because no heat is applied to the ink, and there is no restriction to consider thermal denaturation in the selection of the ink, but the production cost of the head is high for high resolution patterning. It can be disadvantageous in that it rises.
  • the flexography method applies conductive ink on an anilox roller having a uniform grating, spreads it evenly through a doctor blade, and then the anilox roller. It is a method of printing on the surface of the desired substrate by transferring the conductive ink in a pattern embossed on the flexible resin plate of the printing roll by contacting the printing roll.
  • the printed electronic technique may be implemented by spraying a conductive ink on the nanofiber web and sintering the sprayed conductive ink to form a circuit pattern layer on at least one surface of the nanofiber web.
  • the conductive ink may include at least one conductive particle among gold, silver, copper, platinum, palladium, nickel, aluminum, and carbon particles, and considering the conductivity and chemical resistance, gold, silver Platinum is preferable, and silver may be more preferable in consideration of cost and sintering temperature described later.
  • the conductive particles included in the conductive ink are not limited to the above-mentioned metals, and include all metals or nonmetals that can be used as the material of the conductive ink.
  • the conductive particles may be nano or micro scale, and the type of the conductive particles and the content of the conductive ink may be appropriately selected according to the physical properties of the circuit pattern layer.
  • the conductive ink may further include a solvent and a binder for uniform dispersion of the conductive particles and, depending on the intended use and need, contains an additive applied to the printed electronics in a range that does not affect the effect of the present invention. It is possible to let.
  • a viscosity aid, a conductive aid, a chalking inhibitor, an antioxidant, a pH aid, a drying inhibitor, an adhesion agent, a preservative, an antifoaming agent, a leveling agent, a surfactant, and the like can be exemplified.
  • the composition and the ratio of the additional additives may be appropriately selected in consideration of the physical properties of the circuit pattern layer so as to form a uniform circuit pattern layer by evaporating through the sintering process to be described later.
  • the conductive particles included in the conductive ink may be prepared by dispersing them in a solvent as described above. Since the conductive particles are dispersed in a very unstable state, the conductive particles may aggregate again. . In particular, when the conductive particles are used in the nano-size as in the present invention, such agglomeration may cause deterioration of electrical properties, which may result in poor uniformity and electrical conductivity of the circuit pattern layer when the circuit pattern is formed through the printing process. have.
  • sintering may be performed in the step of forming a circuit pattern layer to be described later to form a uniform circuit pattern layer without using a dispersant that specifically controls dispersion.
  • the sprayed conductive ink is sintered to form a circuit pattern layer on at least one surface of the nanofiber web.
  • the forming of the circuit pattern layer is a step of forming a circuit pattern layer by solidifying the conductive ink, and as an additional effect as described above, improves dispersion stability and uniformity of the conductive ink to form a more uniform circuit pattern layer. Step.
  • Sintering refers to a phenomenon in which a powder is bound and solidified when the powder receives strong energy from the outside.
  • the conductive ink composed of the metal particles when the powder is sintered, the particles simply bind to each other to form a particle size. Is not only ideally changed into a thin film form in which no pores exist, but also materials such as additives, which are additionally included on the surface of the metal particles, disappear due to pyrolysis or volatilization to improve dispersion stability, thereby maximizing conductivity characteristics.
  • the ink printed on the substrate may be heat treated using an oven or a furnace.
  • the present invention is not limited thereto, and various known sintering methods may be performed in a range that does not affect the physical properties of the nanofiber web on which the circuit pattern layer is formed.
  • the manufacturing method for implementing a printed circuit nanofiber web according to the present invention can be formed to have a dense and uniform thickness of the circuit pattern portion on the flexible nanofiber web using an electroless plating method and at the same time have a number of pores As it meets the waterproof and breathable characteristics through the nanofiber web, it can be variously applied in various future industrial fields including electronic devices such as medical devices and smart devices such as biopatches.
  • the present invention as shown in Figure 3, of the nanofiber web 100 including a plurality of nanofibers 110 and the nanofibers 110 included in a predetermined region on the nanofiber web 100
  • a printed circuit nanofiber web including a circuit pattern part 120 formed by covering an outer surface is implemented, and the predetermined area is an area A in which the circuit pattern part 120 is to be formed on the nanofiber web 100.
  • the description of the other printed circuit nanofiber web is the same as the description according to the manufacturing method (2) described above will be omitted.
  • the printed circuit nanofiber web according to the present invention not only has significantly improved flexibility and resilience than the conventional flexible printed circuit board, but also has excellent flexibility and elasticity, and thus is utilized as a biopatch in the medical industry which is recently attracting attention.
  • the printed circuit nanofiber web according to the present invention can be manufactured in the form of various sensors that can be attached to virtually any part of the body, thereby promoting the development of related industries by improving the utilization in various industrial fields related to electronic devices including the Internet of Things in the future. .
  • the present invention implements an electronic device including the above-described printed circuit nanofiber web and at least one electronic component mounted on the printed circuit nanofiber web.
  • the electronic component may be appropriately selected according to various industries desired.
  • the electronic component may include a sensor unit including at least one of a biosensor for detecting a user's physical condition and an environmental sensor for sensing a surrounding environment.
  • the electronic device may include a short range communication module used for short range wireless communication, an antenna pattern used for wireless communication, and a control unit for performing a signal processing function.
  • a spinning solution 30 parts by weight of polyurethane is mixed with respect to 100 parts by weight of polyvinylidene fluoride as a fiber forming component, and the weight ratio of dimethylacetamide and acetone is 15:30 of the fiber forming component.
  • a mixed solution was prepared by dissolving 85 g at 80 ° C. using a magnetic bar for 6 hours.
  • the spinning solution was put into a solution tank of an electrospinning apparatus and discharged at a rate of 15 ⁇ l / min / hole.
  • the temperature of the spinning section is 30 °C
  • the humidity is 50%
  • the distance between the collector and the spinning nozzle tip is 20cm
  • a voltage of more than 40kV is applied to the spinning nozzle pack using a high voltage generator.
  • a fiber web formed of PVDF / PU composite nanofibers was prepared by imparting an air pressure of 0.03 MPa per spin pack nozzle.
  • a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. or higher and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web.
  • the prepared nanofiber web has a thickness of 20 ⁇ m, porosity was 55%.
  • a PET film containing a silicone adhesive component is formed through a punching process according to a pattern mold.
  • the prepared PET mask is attached to face two surfaces of the prepared nanofiber web so that only the pattern is exposed to prepare a masked nanofiber web.
  • a metal shell of nickel / copper was formed on the masked nanofiber web.
  • nickel / copper electroless plating was performed on the nanofiber web, and for this purpose, the nanofiber web was immersed in 60 ° C. degreasing solution (ATS condiclean 10%, pure water) for 30 seconds, washed with pure water, and then etched at 60 ° C. It was immersed in the solution (5M NaOH, pure water) for 1 minute and washed with pure water. Thereafter, the washed nanofiber web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water. The nanofiber web was then immersed in 50 ° C.
  • Preparation was carried out in the same manner as in Example 1, but the nickel / copper was deposited by a resistive heating vacuum deposition method, not electroless plating, sputtering was carried out to an average thickness of 0.2 ⁇ m and the photo-lithography process was performed.
  • Photoresist was coated on the surface using a spin coater and then UV was irradiated using a patterned mask. Thereafter, the pattern was immersed in a developer for 30 seconds to form a pattern, and then a circuit pattern part was formed through an etching process to prepare a printed circuit nanofiber web having a line width of 0.3 cm and a length of 10 cm.
  • Example 2 Prepared in the same manner as in Example 1, a printed circuit board was prepared to use a polyimide substrate instead of nanofiber web.
  • the printed circuit nanofiber webs prepared according to the Examples and Comparative Examples were evaluated for the flexibility and the resilience by measuring the variation rate compared to the initial resistance after bending and restoring by 180 ° using a stainless steel rod having a diameter of 30 mm.
  • the elasticity was evaluated by measuring the variation rate compared with the initial resistance after the circuit pattern was stretched 1.2 times in the longitudinal direction using a jig.
  • the resistance of the surface of the printed circuit was measured through a resistance measuring instrument (HIOKI 3540 m ⁇ HITESTER, HIOKI).
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Nano Fiber Web Thickness ( ⁇ m) 20 One 10 150 250 Porosity (%) 55 55 55 55 55 55 Circuit pattern part Thickness ( ⁇ m) 0.2 0.2 0.2 0.2 0.2 0.2 Forming method Electroless Plating Electroless Plating Electroless Plating Electroless Plating Electroless Plating Flexibility and Resilience Rating (%) 3.6 5.3 2.9 18.9 21.6 Elasticity rating (%) 17.4 106.2 42.3 155.3 186.2 Durability rating ⁇ ⁇ ⁇ ⁇ ⁇ Fairness assessment ⁇ ⁇ ⁇ ⁇ ⁇ Resistance ( ⁇ ) 1.21 58.24 0.92 0.47 1.60
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Nano Fiber Web Thickness ( ⁇ m) 20 20 20 20 20 20 20 20 20 20 Porosity (%) 5 30 60 90 55 Circuit pattern part Thickness ( ⁇ m) 0.2 0.2 0.2 0.2 0.05 Forming method Electroless Plating Electroless Plating Electroless Plating Electroless Plating Electroless Plating Flexibility and Resilience Rating (%) 21.4 8.8 3.3 3.2 2.1 Elasticity rating (%) 126.2 55.1 19.2 73.8 71.5 Durability rating ⁇ ⁇ ⁇ ⁇ Fairness assessment ⁇ ⁇ ⁇ ⁇ ⁇ Resistance ( ⁇ ) 1.43 0.84 2.54 147.1 151.7
  • Example 12 Comparative Example 1 Comparative Example 2 Nano Fiber Web Thickness ( ⁇ m) 20 20 20 20 20 20 Porosity (%) 55 55 55 55 PI substrate Circuit pattern part Thickness ( ⁇ m) 3 12 0.2 0.2 Forming method Electroless Plating Electroless Plating Photolithography Electroless Plating Flexibility and Resilience Rating (%) 16.6 31.7 5.1 3.2 Elasticity rating (%) 203.5 532.1 18.6 197.1 Durability rating ⁇ ⁇ ⁇ ⁇ Fairness assessment ⁇ ⁇ ⁇ ⁇ Resistance ( ⁇ ) 0.52 0.31 237.3 18.5
  • Examples 1, 3, 4, 7, 8 and the like satisfying all of the thickness, porosity, circuit pattern portion thickness and circuit pattern portion forming method of the nanofiber web according to the present invention and 11 has excellent flexibility, resilience, elasticity, durability, and fairness as compared to Examples 2, 5, 6, 9, 10, 12, and Comparative Examples 1 to 2, all of which are missing. The minimum value was satisfied but the resistance was significantly lower.

Abstract

A printed circuit nanofiber web manufacturing method is provided. A printed circuit nanofiber web manufacturing method according to an embodiment of the present invention is performed by comprising the steps of: (1) electrospinning a spinning solution comprising a fiber-forming component, thereby manufacturing a nanofiber web; and (2) forming a circuit pattern portion so as to coat the outer surface of a nanofiber included in a predetermined area on the nanofiber web through electroless plating. Accordingly, it is possible to implement a printed circuit nanofiber web having a circuit pattern printed thereon, which has flexibility and restoration characteristics so as to be suitable for a futuristic smart device. In addition, electroless plating can be used to form a circuit pattern portion on a flexible nanofiber web so as to be compact and to have a uniform thickness, and the nanofiber web having multiple pores simultaneously satisfies waterproofing and air-permeating characteristics, making it possible to variously apply the same in various future industrial fields, including medical devices such as bio-patches and electronic devices such as smart devices.

Description

인쇄회로 나노섬유웹 제조방법, 이를 통해 제조된 인쇄회로 나노섬유웹 및 이를 이용한 전자기기Printed circuit nanofiber web manufacturing method, printed circuit nanofiber web manufactured through the same and an electronic device using the same
본 발명은 인쇄회로 나노섬유웹에 관한 것이며, 더욱 상세하게는 가요성, 복원성, 방수성 및 통기성이 있는 인쇄회로 나노섬유웹의 제조방법, 이를 통해 제조된 인쇄회로나노웹 및 이를 이용한 전자기기에 관한 것이다.The present invention relates to a printed circuit nanofiber web, and more particularly, to a method for manufacturing a printed circuit nanofiber web having flexibility, resilience, waterproofness, and breathability, and a printed circuit nanoweb manufactured through the same and an electronic device using the same. will be.
일반적으로 인쇄회로기판(PCB)은 다양한 분야의 전기, 전자제품의 기초가 되는 부품이며, 생활 가전제품은 물론 반도체용 모듈, 검사장치, 자동차, 방위산업 및 인공위성에 이르기까지 인쇄회로기판의 활용도가 점차 확대되어 가고 있다.In general, printed circuit board (PCB) is a basic component of electric and electronic products in various fields, and the utilization of printed circuit boards from not only household appliances but also semiconductor modules, inspection devices, automobiles, defense industries, and satellites It is gradually expanding.
한편, 미래에 개발되어 활용될 미래형 스마트 기기는 현존의 디바이스와는 구조적, 개념적으로 차이가 있을 것으로 예상되며 특히, 최근 스마트 기기는 인체에 착용되어 인간 생활을 편리하게 하기 위한 안경, 의복 등과 전자적인 부품을 함께 내장하여 개발되고 있다. 이러한 변화의 추이 속에 사용자가 착용 가능한 인쇄회로기판의 개발은 스마트 의류와 같은 미래형 디바이스의 개발을 촉진할 수 있으므로, 가요성이 향상되어 인체에 착용이 가능한 인쇄회로기판의 연구 및 기술개발이 반드시 필요하다.On the other hand, future smart devices that will be developed and utilized in the future are expected to be structurally and conceptually different from existing devices. It is developed by embedding parts together. The development of printed circuit boards that can be worn by users in the course of these changes can promote the development of future devices such as smart clothing, so research and technology development of printed circuit boards that can be worn on the human body is essential. Do.
일반적인 인쇄회로기판은 에폭시 수지에 유리 섬유 등의 보강재를 첨가시키고, 동박을 접착시킨 경성인쇄회로기판(Rigid Printed Circuit Board; Rigid PCB), 폴리이미드(polyimide) 기재 상에 동박을 접착시킨 연성인쇄회로기판(Flexible Printed Circuit Board; FPCB) 및 경성인쇄회로기판과 연성인쇄회로기판의 장점을 결합시킨 경성-연성인쇄회로 기판(Rigid- Flexible Printed Circuit Board; R-F PCB)으로 나누어질 수 있으며, 한국 등록특허공보 제10-1139970호(특허 문헌 1)에는 연성의 절연기판 상에 형성된 시드층 상에 회로패턴을 형성하는 1단계; 상기 회로패턴 상에 제1감광물질을 도포하는 2단계; 상기 제1감광물질을 노광, 현상하여 상기 회로패턴 상에 보호패턴을 형성하는 3단계; 상기 시드층을 에칭하는 4단계; 및 상기 보호패턴을 박리하는 5단계를 포함하며, 상기 제1감광물질은 액상 또는 필름형 감광제인 것을 특징으로 하는 플렉서블 인쇄회로기판의 제조방법이 개시되어 있다.A general printed circuit board is a flexible printed circuit in which copper foil is adhered on a rigid printed circuit board (rigid PCB) and a polyimide substrate, in which a reinforcement such as glass fiber is added to an epoxy resin and the copper foil is bonded. Flexible Printed Circuit Board (FPCB) and Rigid-Flexible Printed Circuit Board (RF PCB), which combines the advantages of a rigid printed circuit board and a flexible printed circuit board. Korean Patent Publication No. 10-1139970 (Patent Document 1) includes a step of forming a circuit pattern on a seed layer formed on a flexible insulating substrate; Applying a first photosensitive material on the circuit pattern; Exposing and developing the first photosensitive material to form a protective pattern on the circuit pattern; Etching the seed layer; And a five step of peeling the protective pattern, wherein the first photosensitive material is a liquid or film type photosensitive agent.
상기 특허문헌 1의 제조방법을 이용하면 가요성이 있는 인쇄회로기판을 구현할 수 있으나, 베이스부재가 폴리이미드 필름과 같은 연성의 절연기판이므로, 충분한 가요성을 가지지 못하고, 접히거나 구겨진 후 다시 펴지는 복원 특성 또한 기대할 수 없으며, 통기성을 가지지 못하여 웨어러블이 요구되는 스마트 기기 등에는 적용할 수 없는 단점이 있다.When using the manufacturing method of the patent document 1 can implement a flexible printed circuit board, but since the base member is a flexible insulating substrate such as polyimide film, it does not have sufficient flexibility, it is folded or folded after being unfolded Restoration characteristics are also not expected, and there is a drawback that it is not applicable to smart devices that do not have breathability and require wearables.
이에 가요성, 복원성 및 통기성을 가짐과 동시에 착용 가능한 형태로 제작되어 유연한 전자 소자 또는 미래형 웨어러블 스마트기기에도 적용이 가능한 인쇄회로기판에 대한 기술 개발이 시급한 실정이다.Accordingly, there is an urgent need to develop a technology for a printed circuit board that has flexibility, resilience, and breathability and is applicable to a flexible electronic device or a future wearable smart device.
본 발명은 상기와 같은 점을 감안하여 안출된 것으로, 나노섬유웹에 회로패턴을 인쇄하여 가요성 및 복원성을 가지는 인쇄회로기판의 제조 방법 및 이를 이용한 전자 기기를 제공하는데 발명의 목적이 있다.The present invention has been made in view of the above, and an object of the present invention is to provide a method of manufacturing a printed circuit board having flexibility and resilience by printing a circuit pattern on a nanofiber web and an electronic device using the same.
또한, 본 발명은, 회로패턴부의 치밀성 및 두께 균일성을 향상시키고 나노섬유웹과 같은 유연한 기재에 회로패턴부를 도금할 수 있는 무전해도금법을 이용한 인쇄회로기판의 제조 방법 및 이를 이용한 전자 기기를 제공하는데 발명의 다른 목적이 있다.In addition, the present invention provides a method of manufacturing a printed circuit board using an electroless plating method which can improve the compactness and thickness uniformity of the circuit pattern portion and plate the circuit pattern portion on a flexible substrate such as a nanofiber web, and an electronic device using the same. There is another object of the invention.
더불어, 본 발명은 나노 사이즈의 섬유가 축적되어 형성된 다수의 기공을 가지는 나노섬유웹을 인쇄회로기판의 베이스 기재로 적용하여 바이오 패치 또는 의료용 센서에 요구되는 가요성, 복원성 및 통기성을 만족하는 인쇄회로기판의 제조 방법 및 이를 이용한 전자 기기를 제공하는데 발명의 또 다른 목적이 있다.In addition, the present invention by applying a nanofiber web having a plurality of pores formed by the accumulation of nano-sized fibers as the base substrate of the printed circuit board printed circuit that satisfies the flexibility, resilience and breathability required for bio patch or medical sensor Another object of the present invention is to provide a method of manufacturing a substrate and an electronic device using the same.
상술한 과제를 해결하기 위하여 본 발명은 (1) 섬유형성성분이 포함된 방사용액을 전기 방사하여 나노섬유웹을 제조하는 단계; 및 (2) 무전해도금법을 통해 상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하도록 회로패턴부를 형성시키는 단계;를 포함하는 인쇄회로 나노섬유웹의 제조방법을 제공한다.In order to solve the above problems, the present invention comprises the steps of (1) preparing a nanofiber web by electrospinning a spinning solution containing a fiber forming component; And (2) forming a circuit pattern portion to cover an outer surface of the nanofibers included in a predetermined region on the nanofiber web by an electroless plating method.
또한, 본 발명의 일 실시예에 의하면 상기 나노섬유웹은 두께가 5 ~ 200㎛일 수 있다.In addition, according to an embodiment of the present invention, the nanofiber web may have a thickness of 5 to 200 μm.
또한, 상기 나노섬유웹은 기공도가 10 ~ 80%일 수 있다.In addition, the nanofiber web may have a porosity of 10 to 80%.
또한, 상기 나노섬유에 피복된 회로패턴부의 두께는 0.1 ~ 10㎛일 수 있다.In addition, the thickness of the circuit pattern portion coated on the nanofibers may be 0.1 ~ 10㎛.
또한, 상기 나노섬유웹은 두께가 10 ~ 150㎛ 및 기공도가 30 ~ 60%일 수 있고, 상기 나노섬유에 피복된 회로패턴부의 두께는 0.1 ~ 3㎛일 수 있다.In addition, the nanofiber web may have a thickness of 10 to 150㎛ and porosity of 30 to 60%, the thickness of the circuit pattern portion coated on the nanofiber may be 0.1 to 3㎛.
또한, 상기 (2) 단계는, 2-1) 상기 나노섬유웹을 촉매 용액에 침지시켜 촉매화 처리하는 단계; 2-2) 촉매화 처리된 상기 나노섬유웹을 활성화시키는 단계; 및 2-3) 활성화된 상기 나노섬유웹을 무전해도금법을 통해 회로패턴부를 형성시키는 단계;를 더 포함할 수 있다.In addition, the step (2), 2-1) immersing the nanofiber web in a catalyst solution to catalyze the treatment; 2-2) activating the catalyzed nanofiber web; And 2-3) forming the circuit pattern part by electroless plating the activated nanofiber web.
또한, 상기 (2) 단계를 수행하기 전에, 상기 나노섬유웹을 탈지시키거나 친수화 처리하는 단계;를 더 포함할 수 있다.In addition, before performing the step (2), the step of degreasing or hydrophilizing the nanofiber web; may further include.
또한, 상기 촉매 용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe의 염으로 이루어진 군에서 선택되는 어느 하나 이상의 화합물을 포함할 수 있다.In addition, the catalyst solution may include any one or more compounds selected from the group consisting of salts of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
또한, 상기 2-2) 단계는, 황산용액에 침지하여 활성화시키는 단계일 수 있다.In addition, step 2-2) may be a step of activating by immersing in sulfuric acid solution.
또한, 상기 (2) 단계에 따른 무전해도금법은 상기 나노섬유웹 상에 회로패턴부가 형성될 부분을 제외한 나머지 면을 마스킹하여 도금용액에 침지시키는 단계일 수 있다.In addition, the electroless plating method according to step (2) may be a step of immersing in the plating solution by masking the remaining surface except for the portion where the circuit pattern portion is to be formed on the nanofiber web.
또한, 상기 도금용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe로 이루어진 군에서 선택되는 금속을 포함할 수 있다.In addition, the plating solution may include a metal selected from the group consisting of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
또한, 상기 인쇄회로 나노섬유웹은 회로패턴부에 의해 형성되는 상부영역의 제1패턴과 하부영역의 제2패턴을 각각 포함할 수 있고, 상기 제1패턴과 제2패턴은 서로 동일한 패턴으로 형성될 수 있다.In addition, the printed circuit nanofiber web may include a first pattern of the upper region and a second pattern of the lower region formed by the circuit pattern portion, respectively, wherein the first pattern and the second pattern are formed in the same pattern Can be.
또한, 상기 회로패턴부는 상기 나노섬유웹의 상부면에 형성된 제1회로패턴부 및 하부면에 형성된 제2회로패턴부를 포함할 수 있고, 상기 제1회로패턴부 및 제2회로패턴부는 서로 동일한 회로패턴으로 형성될 수 있다.In addition, the circuit pattern portion may include a first circuit pattern portion formed on the upper surface of the nanofiber web and a second circuit pattern portion formed on the lower surface, wherein the first circuit pattern portion and the second circuit pattern portion are the same circuit It can be formed in a pattern.
또한, 인쇄회로 나노섬유웹은 회로패턴부가 인쇄된 나노섬유웹 일면에 대향하는 면에 강도보강용 지지체를 더 구비할 수 있다.In addition, the printed circuit nanofiber web may further include a strength reinforcing supporter on a surface facing the one surface of the nanofiber web printed circuit pattern portion.
또한, 상기 섬유형성성분은 폴리우레탄(polyurethane), 폴리스티렌(polystylene), 폴리비닐알코올(polyvinylalchol), 폴리메틸메타크릴레이트(polymethyl methacrylate), 폴리락트산(polylactic acid), 폴리에틸렌옥사이드(polyethyleneoxide), 폴리비닐아세테이트(polyvinyl acetate), 폴리아크릴산(polyacrylic acid), 폴리카프로락톤(polycaprolactone), 폴리아크릴로니트릴(polyacrylonitrile), 폴리비닐피롤리돈(polyvinylpyrrolidone), 폴리염화비닐(polyvinylchloride), 폴리카보네이트(polycarbonate), 폴리이더이미드(polyetherimide), 폴리이더술폰(polyesthersulphone), 폴리벤지미다졸(polybenzimidazol), 폴리에틸렌테레프탈레이트(polyethylene terephthalate), 폴리부틸렌테레프탈레이트(polybutylene terephthalate) 및 불소계화합물로 이루어진 군에서 선택된 1종 이상의 화합물을 포함할 수 있다.In addition, the fiber forming component is polyurethane (polyurethane), polystyrene (polystylene), polyvinyl alcohol (polyvinylalchol), polymethyl methacrylate (polymethyl methacrylate), polylactic acid (polylactic acid), polyethylene oxide (polyethyleneoxide), polyvinyl Acetate (polyvinyl acetate), polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl chloride, polycarbonate, At least one member selected from the group consisting of polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate and fluorine-based compounds It may include a compound.
또한, 본 발명은 다수 개의 나노섬유를 포함하는 나노섬유웹; 및 상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하여 형성되는 회로패턴부;를 포함하는 인쇄회로 나노섬유웹을 제공한다.The present invention also provides a nanofiber web comprising a plurality of nanofibers; And a circuit pattern portion formed by covering an outer surface of the nanofibers included in a predetermined region on the nanofiber web.
또한, 본 발명은 상술한 인쇄회로 나노섬유웹; 및 상기 인쇄회로 나노섬유웹에 실장된 적어도 하나 이상의 전자 부품;을 포함하는 전자장치를 제공한다.In addition, the present invention is the printed circuit nanofiber web; And at least one electronic component mounted on the printed circuit nanofiber web.
본 발명에 따른 인쇄회로 나노섬유웹의 제조방법에 의하면, 미래형 스마트 기기에 적합하도록 가요성 및 복원성을 가지는 회로패턴이 인쇄된 인쇄회로 나노섬유웹을 구현할 수 있다. 또한, 무전해도금법을 이용하여 유연한 나노섬유웹 상에 회로패턴부가 치밀하고 균일한 두께를 가지도록 형성할 수 있는 동시에 다수의 기공을 가지는 나노섬유웹을 통해 방수성과 통기성 특성을 만족함에 따라서 바이오패치 등의 의료기기, 스마트기기 등의 전자기기를 포함하여 각종 미래산업분야에서 다양하게 응용될 수 있다.According to the method of manufacturing a printed circuit nanofiber web according to the present invention, a printed circuit nanofiber web having a printed circuit pattern having flexibility and resilience can be implemented to be suitable for future smart devices. In addition, by using the electroless plating method, the circuit pattern portion can be formed on the flexible nanofiber web to have a dense and uniform thickness, and at the same time, the biopatch is satisfied by satisfying the waterproof and breathable characteristics through the nanofiber web having a plurality of pores. It can be applied in various future industries, including electronic devices such as medical devices, smart devices, and the like.
도 1는 종래 증착-리소그래피 공정을 나타내는 도면,1 shows a conventional deposition-lithography process,
도 2는 본 발명의 일 실시예에 의한 무전해도금법을 나타내는 순서도,2 is a flowchart showing an electroless plating method according to an embodiment of the present invention;
도 3은 본 발명의 일 실시예에 따라 나노섬유웹 소정의 영역 상에 회로패턴부가 형성된 모습을 나타내는 모식도,3 is a schematic diagram showing a circuit pattern formed on a predetermined region of the nanofiber web according to an embodiment of the present invention,
도 4는 도 3에 도시된 X-X' 경계선에 따른 나노섬유의 단면을 나타내는 사시도,4 is a perspective view showing a cross section of the nanofiber along the X-X 'boundary line shown in FIG.
도 5 내지 도 7은 도금조건을 달리하여 도금된 회로패턴부의 두께를 나타내는 주사전자현미경 사진으로써, 도 5는 나노섬유에 도금된 회로패턴부의 두께가 가장 얇게 피복된 모습을 나타내고, 도 6a 및 6b는 도 5 대비 나노섬유에 도금된 회로패턴부의 두께가 두껍게 피복된 모습을 나타내고, 도 7a 및 7b는 나노섬유에 도금된 회로패턴부의 두께가 가장 두껍게 피복된 모습을 나타내며, 그리고5 to 7 are scanning electron micrographs showing the thickness of the circuit pattern portion plated by varying the plating conditions, Figure 5 is a view showing the thinnest coating thickness of the circuit pattern portion plated on the nanofiber, Figures 6a and 6b 5 shows a thick coating of the circuit pattern portion plated on the nanofibers, and FIGS. 7A and 7B show the thickest coating of the thickness of the circuit pattern portion plated on the nanofibers, and
도 8 및 도 9는 본 발명의 일 실시예에 따른 제조방법으로 제조된 인쇄회로 나노섬유웹을 나타내는 도면이다.8 and 9 are views showing a printed circuit nanofiber web manufactured by the manufacturing method according to an embodiment of the present invention.
이하, 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성요소에 대해서는 동일한 참조부호를 부가한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.
본 발명에 따른 인쇄회로 나노섬유웹의 제조방법은 (1) 섬유형성성분이 포함된 방사용액을 전기 방사하여 나노섬유웹을 제조하는 단계; 및 (2) 무전해도금법을 통해 상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하도록 회로패턴부를 형성시키는 단계;를 포함하여 수행된다.The method of manufacturing a printed circuit nanofiber web according to the present invention comprises the steps of: (1) preparing a nanofiber web by electrospinning a spinning solution containing a fiber forming component; And (2) forming a circuit pattern portion to cover the outer surface of the nanofibers included in the predetermined region on the nanofiber web by electroless plating.
상기 (1) 단계는 섬유형성성분이 포함된 방사용액을 전기 방사하여 회로패턴부를 구비하는 나노섬유웹을 제조하는 단계이다. 본 발명의 제조방법에 따른 (1) 단계를 설명하기에 앞서서, 회로패턴부를 형성시키는 기재로써 나노섬유웹을 사용하는 이유에 대하여 먼저 설명하기로 한다.Step (1) is a step of producing a nanofiber web having a circuit pattern portion by electrospinning the spinning solution containing the fiber forming component. Prior to describing step (1) according to the manufacturing method of the present invention, the reason for using the nanofiber web as a substrate for forming the circuit pattern portion will be described first.
일반적인 인쇄회로기판은 에폭시 수지에 유리 섬유 등의 보강재를 첨가시키고, 동박을 접착시킨 경성인쇄회로기판(Rigid Printed Circuit Board; Rigid PCB), 폴리이미드(polyimide) 기재 상에 동박을 접착시킨 연성인쇄회로기판(Flexible Printed Circuit Board; FPCB) 및 경성인쇄회로기판과 연성인쇄회로기판의 장점을 결합시킨 경성-연성인쇄회로 기판(Rigid- Flexible Printed Circuit Board; R-F PCB)으로 나누어질 수 있다. 특히 최근 추세를 반영한 스마트 기기와 같은 미래형 디바이스용 인쇄회로기판의 경우, 우수한 가요성이 요구되며 접거나 구겨지더라도 원래의 편평한 상태를 유지할 수 있는 복원력 및 높은 휘어짐 특성이 요구된다. 그러나 종래의 연성인쇄회로기판에 사용되는 폴리이미드는 일정 수준의 가요성을 가지고 있으나, 접거나 구겨지면 다시 원래의 편평한 상태로 돌아가는 복원력이 매우 낮으며, 휘어짐에도 취약한 특성을 나타냄에 따라 미래형 디바이스에 는 다소 부적절한 면이 있다.A general printed circuit board is a flexible printed circuit in which copper foil is adhered on a rigid printed circuit board (rigid PCB) and a polyimide substrate, in which a reinforcement such as glass fiber is added to an epoxy resin and the copper foil is bonded. It can be divided into a flexible printed circuit board (FPCB) and a rigid-flexible printed circuit board (RF PCB) that combines the advantages of a flexible printed circuit board and a flexible printed circuit board. In particular, in the case of printed circuit boards for future devices such as smart devices reflecting the recent trend, excellent flexibility is required, and resilience and high bending characteristics that can maintain the original flat state even when folded or wrinkled are required. However, the polyimide used in the conventional flexible printed circuit board has a certain level of flexibility, but when folded or creased, the polyimide has a very low resilience to return to its original flat state, and is vulnerable to warpage, thus making it difficult for future devices. Is somewhat inadequate.
이에 본 발명은 다수 개의 나노섬유가 랜덤하게 축적되어 이루어지는 나노섬유웹에 회로패턴을 인쇄하는 제조방법을 통해 상술한 미래형 스마트 기기에 적합하도록 우수한 가요성과 복원성을 가짐과 동시에 우수한 휘어짐 특성을 나타내는 인쇄회로 나노섬유웹을 구현한다.Accordingly, the present invention provides a printed circuit having excellent flexibility and resilience and excellent bending characteristics to be suitable for the future smart devices through a manufacturing method of printing a circuit pattern on a nanofiber web in which a plurality of nanofibers are randomly accumulated. Implement nanofiber web.
즉, 본 발명에 따른 제조방법으로 구현되는 인쇄회로 나노섬유웹은 도 2에 도시된 순서도와 같이, 나노섬유웹을 구성하는 나노섬유의 외부표면을 감싸도록 회로패턴부를 형성하여, 나노섬유 자체의 우수한 가요성을 충분히 활용할 수 있으며, 랜덤하게 적층된 상기 나노섬유로 인해 접히거나 구겨진 이후 다시 회복되는 복원 특성도 향상될 수 있다. 나아가, 웹 구조의 시트를 구현됨에 따라 초경박 기기나 웨어러블 디바이스 등의 미래 지향적인 디바이스로의 활용도를 제고할 수 있다.That is, the printed circuit nanofiber web implemented by the manufacturing method according to the present invention forms a circuit pattern portion to surround the outer surface of the nanofibers constituting the nanofiber web, as shown in the flow chart shown in Figure 2, The excellent flexibility can be fully utilized, and the recovery property of being restored after being folded or wrinkled due to the randomly stacked nanofibers can be improved. Furthermore, as the sheet of the web structure is implemented, it is possible to improve the utilization as a future-oriented device such as ultrathin devices or wearable devices.
상기 나노섬유웹은 나노섬유를 구비하여 3차원 네트워크 형상의 섬유웹을 형성시키는 방법의 경우 제한 없이 사용될 수 있다. 바람직하게는 상기 나노섬유웹은 섬유형성성분을 포함하는 방사용액을 전기방사 하여 나노섬유웹을 형성할 수 있다.The nanofiber web may be used without limitation in the case of a method of forming a fibrous web having a three-dimensional network shape by providing a nanofiber. Preferably, the nanofiber web may form a nanofiber web by electrospinning a spinning solution containing a fiber forming component.
상기 나노섬유웹을 제조하기 위한 방사용액에 포함되는 섬유형성성분은 당업계에서 통상적으로 사용할 수 있는 섬유형성성분이라면 제한 없이 사용할 수 있으며, 바람직하게는 폴리우레탄(polyurethane), 폴리스티렌(polystylene), 폴리비닐알코올(polyvinylalchol), 폴리메틸메타크릴레이트(polymethyl methacrylate), 폴리락트산(polylactic acid), 폴리에틸렌옥사이드(polyethyleneoxide), 폴리비닐아세테이트(polyvinyl acetate), 폴리아크릴산(polyacrylic acid), 폴리카프로락톤(polycaprolactone), 폴리아크릴로니트릴(polyacrylonitrile), 폴리비닐피롤리돈(polyvinylpyrrolidone), 폴리염화비닐(polyvinylchloride), 폴리카보네이트(polycarbonate), 폴리이더이미드(polyetherimide), 폴리이더술폰(polyesthersulphone), 폴리벤지미다졸(polybenzimidazol), 폴리에틸렌테레프탈레이트(polyethylene terephthalate), 폴리부틸렌테레프탈레이트(polybutylene terephthalate) 및 불소계화합물로 이루어진 군에서 선택된 1종 이상의 화합물을 포함할 수 있다.The fiber forming component included in the spinning solution for manufacturing the nanofiber web can be used without limitation as long as it is a fiber forming component that can be commonly used in the art, preferably polyurethane, polystyrene, poly Polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethyleneoxide, polyvinyl acetate, polyacrylic acid, polycaprolactone , Polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyetherimide, polyethersulphone, polybenzimidazole polybenzimidazol), polyethylene terephthalate, polybutylene terephthalate It may comprise at least one compound selected from the group consisting of (polybutylene terephthalate), and fluorine-based compound.
또한, 상기 불소계 화합물은 폴리테트라플루오로에틸렌(PTFE)계, 테트라플루오로에틸렌-퍼플루오로알킬 비닐 에테르 공중합체(PFA)계, 테트라플루오로에틸렌-헥사플루오로프로필렌 공중합체(FEP)계, 테트라플루오로에틸렌-헥사플루오로프로필렌-퍼플루오로알킬 비닐 에테르 공중합체(EPE)계, 테트라플루오로에틸렌-에틸렌 공중합체(ETFE)계, 폴리클로로트리플루오로에틸렌(PCTFE)계, 클로로트리플루오로에틸렌-에틸렌 공중합체(ECTFE)계 및 폴리비닐리덴플루오라이드(PVDF)계로 이루어진 군에서 선택된 1종 이상의 화합물을 포함할 수 있으며, 바람직하게는 폴리비닐리덴플루오라이드(PVDF)를 포함할 수 있다.In addition, the fluorine-based compound is polytetrafluoroethylene (PTFE) -based, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) -based, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) -based, Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE) system, tetrafluoroethylene-ethylene copolymer (ETFE) system, polychlorotrifluoroethylene (PCTFE) system, chlorotrifluoro It may include one or more compounds selected from the group consisting of a low ethylene-ethylene copolymer (ECTFE) system and a polyvinylidene fluoride (PVDF) system, preferably may include a polyvinylidene fluoride (PVDF). .
이때, 상기 나노섬유가 섬유형성성분으로 PVDF를 포함할 경우 상기 PVDF의 중량평균분자량은 10,000 ~ 1,000,000일 수 있고, 바람직하게는 300,000 ~ 600,000일 수 있으나 이에 제한되는 것은 아니다.In this case, when the nanofibers include PVDF as a fiber forming component, the weight average molecular weight of the PVDF may be 10,000 to 1,000,000, preferably 300,000 to 600,000, but is not limited thereto.
상기 섬유형성성분은 방사용액에 5 ~ 30 중량%, 바람직하게는 8 ~ 20 중량%로 포함될 수 있다. 만일 섬유형성성분이 5 중량% 미만일 경우 섬유로 형성되기 어려우며, 방사 시 섬유상으로 방사되지 않고, 액적상태로 분사되어 방사가 이루어지더라도 비드가 많이 형성되고 용매의 휘발이 잘 이루어지지 않아 기공이 막히는 현상이 발생할 수 있다. 또한, 만일 섬유형성성분이 30 중량% 초과할 경우 점도가 상승하여 용액 표면에서 고화가 일어나 장시간 방사가 곤란하며, 섬유직경이 증가하여 마이크로미터 이하 크기의 섬유상을 만들 수 없을 수 있다.The fiber forming component may be included in 5 to 30% by weight, preferably 8 to 20% by weight in the spinning solution. If the fiber-forming component is less than 5% by weight, it is difficult to form a fiber, and when spun, it is not spun into fiber, but even when spun and spun in a droplet, beads are formed and volatilization of the solvent does not occur so that pores are blocked. Symptoms may occur. In addition, if the fiber-forming component is more than 30% by weight, the viscosity rises and solidification occurs at the surface of the solution, which makes it difficult to spin for a long time, and the fiber diameter may increase, making it impossible to form a fibrous size of micrometer or less.
또한, 상기 방사용액은 용매를 더 포함할 수 있고, 상기 용매는 섬유형성성분의 침전물을 생성시키지 않고 후술하는 나노섬유의 방사성에 영향을 미치지 않는 용매의 경우 제한 없이 사용될 수 있으며, 바람직하게는 γ-부티로락톤, 사이클로헥사논, 3-헥사논, 3-헵타논, 3-옥타논, N-메틸피롤리돈, 디메틸아세트아미드, 아세톤 디메틸설폭사이드, 디메틸포름아마이드로 이루어진 군에서 선택된 어느 하나 이상을 포함할 수 있다. 일예로 상기 용매는 디메틸아세트아미드와 아세톤의 혼합용매일 수 있다.In addition, the spinning solution may further include a solvent, the solvent may be used without limitation in the case of a solvent that does not produce a precipitate of the fiber-forming component and does not affect the radioactivity of the nanofibers described later, preferably γ Any one selected from the group consisting of -butyrolactone, cyclohexanone, 3-hexanone, 3-heptanone, 3-octanone, N-methylpyrrolidone, dimethylacetamide, acetone dimethyl sulfoxide, dimethylformamide It may contain the above. For example, the solvent may be a mixed solvent of dimethylacetamide and acetone.
상기 제조된 방사용액은 공지된 전기방사장치 및 방법을 통해 나노섬유를 제조할 수 있다. 일 예로, 상기 전기방사장치는 방사 노즐이 1개인 단일 방사팩을 구비한 전기방사장치를 사용하거나 양산성을 위하여 단일 방사팩 복수개로 구비하거나 노즐이 복수개인 방사팩을 구비한 전기방사 장치를 사용해도 무방하다. 또한 전기방사 방식에 있어서 건식방사 또는 외부응고조를 구비하는 습식방사를 이용할 수 있고 방식에 따른 제한은 없다.The prepared spinning solution may produce nanofibers through known electrospinning devices and methods. For example, the electrospinning device uses an electrospinning device having a single spinning pack having one spinning nozzle or a plurality of single spinning packs for mass production, or an electrospinning device having a spinning pack having a plurality of nozzles. It is okay. In addition, in the electrospinning method, dry spinning or wet spinning having an external coagulation bath can be used, and there is no limitation according to the method.
상기 전기방사장치에 교반시킨 방사용액을 투입시켜 콜렉터, 일예로 종이 상에 전기방사시킬 경우 나노섬유로 형성된 나노섬유웹을 수득할 수 있다. 상기 전기방사를 위한 구체적 조건은 일 예로써, 방사팩의 노즐에 구비되는 에어분사 노즐은 에어 분사의 에어압은 0.01 ~ 0.2MPa 범위로 설정될 수 있다. 만약 에어압이 0.01MPa 미만인 경우 포집, 집적에 기여를 하지 못하며, 0.2MPa를 초과하는 경우 방사노즐의 콘을 굳게 하여 니들을 막는 현상이 발생하여 방사 트러블이 발생할 수 있다. 또한, 상기 방사용액을 방사할 때, 노즐 당 방사용액의 주입속도는 10 ~ 30㎕/min일 수 있다. 또한, 상기 노즐의 팁과 콜렉터까지의 거리는 10 ~ 30㎝일 수 있다. 다만, 이에 제한되는 것은 아니며 목적에 따라 변경하여 실시할 수 있다.When the stirred spinning solution is added to the electrospinning apparatus, a nanofiber web formed of nanofibers may be obtained when electrospinning onto a collector, for example, paper. Specific conditions for the electrospinning is one example, the air spray nozzle provided in the nozzle of the spinning pack may be set to the air pressure of the air injection is 0.01 ~ 0.2MPa range. If the air pressure is less than 0.01MPa, it does not contribute to the collection and accumulation. If the air pressure exceeds 0.2MPa, the cone of the spinning nozzle is hardened to block the needle, which may cause radiation trouble. In addition, when spinning the spinning solution, the injection rate of the spinning solution per nozzle may be 10 ~ 30㎛ / min. In addition, the distance between the tip of the nozzle and the collector may be 10 ~ 30cm. However, the present invention is not limited thereto, and may be changed according to the purpose.
상기 (1) 단계를 수행하여 제조되는 나노섬유웹은 두께가 5 ~ 200㎛, 바람직하게는 두께가 10 ~ 150㎛일 수 있다. 만일 상기 나노섬유웹의 두께가 5㎛ 미만이면 나노섬유웹에 구비되는 나노섬유의 외부면에 피복된 회로패턴부에 대한 지지기능이 저하될 수 있고, 인쇄회로 나노섬유웹의 내구성 및 기계적 물성이 저하될 수 있다 .또한, 상기 나노섬유웹의 두께가 200㎛를 초과하면 무전해도금 과정에서 발생한 공기가 나노섬유웹 내에서 빠져나가지 못할 수 있고, 내구성 및 공정성이 저하될 수 있으며, 박형화에 불리할 수 있다.Nanofiber web prepared by performing step (1) may have a thickness of 5 ~ 200㎛, preferably 10 ~ 150㎛ thickness. If the thickness of the nanofiber web is less than 5㎛ the support function for the circuit pattern portion coated on the outer surface of the nanofiber provided in the nanofiber web may be reduced, the durability and mechanical properties of the printed circuit nanofiber web In addition, if the thickness of the nanofiber web exceeds 200㎛, air generated during the electroless plating process may not escape in the nanofiber web, durability and processability may be lowered, it is disadvantageous for thinning can do.
또한, 상기 나노섬유웹은 기공도가 10 ~ 80%, 바람직하게는 30 ~ 60%일 수 있다. 만일 상기 나노섬유웹의 기공도가 10% 미만이면 신축성이 저하될 수 있고, 무전해도금 시 섬유웹의 박리현상이 발생할 수 있으며, 내구성이 저하될 수 있고, 기공도가 80%를 초과하면 인쇄회로 나노섬유웹의 내구성, 공정성 및 기계적 물성이 저하될 수 있고, 전기적 특성이 저하될 수 있다.In addition, the nanofiber web may have a porosity of 10 to 80%, preferably 30 to 60%. If the porosity of the nanofiber web is less than 10% may reduce the elasticity, peeling phenomenon may occur when the electroless plating, durability may be reduced, if the porosity exceeds 80% printing Durability, processability and mechanical properties of the circuit nanofiber web may be degraded, and electrical properties may be degraded.
한편, 상기 나노섬유웹 자체의 부족한 강도를 보강하여 상기 나노섬유웹 상에 형성되는 회로패턴부의 안정성을 향상시키기 위해, 후술하는 인쇄회로 나노섬유웹에서 회로패턴부가 인쇄된 나노섬유웹 일면에 대향하는 면에 강도보강용 지지체를 더 구비할 수 있다. 이때, 상기 강도보강용 지지체의 일면에 또는 양면에 적층된 제1나노섬유웹 또는 제2나노섬유웹을 포함하여 구현될 수 있으나, 이에 제한되는 것은 아니다.On the other hand, in order to enhance the stability of the circuit pattern portion formed on the nanofiber web by reinforcing the insufficient strength of the nanofiber web itself, in the printed circuit nanofiber web to be described later is opposed to one surface of the printed nanofiber web The surface may further include a support for strength reinforcement. At this time, it may be implemented including a first nanofiber web or a second nanofiber web laminated on one side or both sides of the strength reinforcing support, but is not limited thereto.
한편, 종래 일반적인 인쇄회로기판의 제조방법은 도 1에 도시된 것과 같이 (a) 내지 (g) 단계의 포토-리소그래피 공정을 이용하며, 이때 금속 입자로 기재 표면에 시드층을 형성하는 공정은 스퍼터링 공정과 같이 일정 압력의 외력을 가하기 때문에, 나노섬유와 같이 유연한 소재의 기재에는 회로패턴부를 형성하기 어려우며, 형성시킨다 하더라도 회로패턴과 접하는 나노섬유 표면이 손상되거나 요철이 형성되어 회로패턴과의 접착성이 저하됨으로 인한 전기전도 특성이 떨어질 수 있어서 이를 이용한 전자 부품의 신뢰성이 떨어질 수 있다.Meanwhile, a conventional method of manufacturing a printed circuit board uses a photo-lithography process of steps (a) to (g) as shown in FIG. 1, wherein the process of forming a seed layer on the surface of the substrate using metal particles is sputtering. As it applies external force under a certain pressure as in the process, it is difficult to form a circuit pattern part on a substrate of a flexible material such as nanofiber, and even if it is formed, the surface of the nanofiber contacting the circuit pattern is damaged or irregularities are formed, thereby adhering to the circuit pattern. Due to this deterioration, the electrical conductivity may be deteriorated, and thus the reliability of the electronic component using the same may be deteriorated.
이에, 본 발명에 따른 제조방법의 (2) 단계는 무전해도금법을 통해 상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하도록 회로패턴부를 형성한다.Thus, step (2) of the manufacturing method according to the present invention forms a circuit pattern portion to cover the outer surface of the nanofibers included in a predetermined region on the nanofiber web through the electroless plating method.
무전해도금법은 외부에서 전기를 가하지 않고도 용액 내에 존재하는 물질들의 자발적인 산화환원반응에 의하여 금속피막이 형성되는 것을 이용한 기술로써, 본 발명에 따른 나노섬유웹에 회로패턴부를 형성하기 위해 상기 무전해도금법을 이용하게 되면 다음과 같은 장점이 있다.The electroless plating method is a technique in which a metal film is formed by spontaneous redox reaction of materials existing in a solution without applying electricity from the outside. The electroless plating method is used to form a circuit pattern portion on a nanofiber web according to the present invention. It has the following advantages.
첫 번째, 도금된 회로패턴부의 균일성을 일정하게 유지시킬 수 있어서 전기전도 특성 및 이를 이용한 전자 부품의 신뢰성을 제고할 수 있다. 즉, 금속피막을 형성하기 위한 일반적인 포토-리소그래피 공정 또는 전기 도금법과는 달리, 무전해도금법은 환원 반응을 이용하여 금속을 석출시키므로 기재 표면에 금속 피막이 균일하게 형성될 수 있으며, 이로 인한 제품형상의 균일성은 물론 전자 부품의 안정성을 향상시킬 수 있다. 다만 균일한 회로패턴부 형성을 위해 금속 도금용액의 균일성이 담보되어야 하며, 또한 산화피막이 형성되어 요철이 발생하는 것을 방지하기 위해 후술하는 활성화 단계를 수행할 수 있다.First, the uniformity of the plated circuit pattern portion can be kept constant, thereby improving electrical conductivity characteristics and reliability of electronic components using the same. That is, unlike a general photo-lithography process or electroplating method for forming a metal film, the electroless plating method precipitates metal by using a reduction reaction, so that a metal film may be uniformly formed on the surface of the substrate, thereby resulting in a product shape. The uniformity as well as the stability of the electronic component can be improved. However, in order to form a uniform circuit pattern part, the uniformity of the metal plating solution should be ensured, and an activation layer described below may be performed to prevent the occurrence of irregularities due to the formation of an oxide film.
두 번째, 무전해도금법을 통한 회로패턴부의 두께를 용이하게 조절할 수 있어서 다양한 산업군에 활용도를 높일 수 있다. 즉, 무전해도금법은 도금용액 내에 존재하는 물질이 기재표면에서의 산화환원반응을 이용하기 때문에 반응 온도와 pH를 조절하여 환원되는 금속의 석출속도를 제어할 수 있으므로 회로패턴부의 두께를 보다 용이하게 조절할 수 있다. 일 예에 따라 니켈 도금용액을 무전해도금법을 통해 도금시키는 경우, pH 4 ~ 6 범위에서 가장 높은 석출속도를 가지기 때문에, 적정 pH 조절을 통해 회로패턴부의 두께를 조절할 수 있다. 다만 일반적으로 금속이 환원될 수 있는 도금용액의 수명은 pH가 낮을수록 길기 때문에 석출속도와 도금용액의 수명 및 회로패턴부의 두께를 고려하여 목적하는 산업군에 적합하도록 적절히 설계할 수 있다.Second, the thickness of the circuit pattern portion through the electroless plating method can be easily adjusted to increase the utilization in various industries. That is, in the electroless plating method, since the material present in the plating solution uses a redox reaction on the surface of the substrate, it is possible to control the deposition rate of the reduced metal by controlling the reaction temperature and pH, thereby making the thickness of the circuit pattern portion easier. I can regulate it. When the nickel plating solution is plated through the electroless plating method according to an example, since it has the highest precipitation rate in the range of pH 4 to 6, the thickness of the circuit pattern portion may be adjusted through proper pH control. However, in general, since the life of the plating solution capable of reducing metal is longer as the pH is lower, the plating solution can be appropriately designed to suit the desired industrial group in consideration of the deposition rate, the life of the plating solution, and the thickness of the circuit pattern part.
세 번째, 무전해도금법을 통하여 다량의 나노섬유웹에 동시에 회로패턴부를 형성할 수 있어 공정 단순화 및 원가 절감의 효과를 얻을 수 있다. 즉, 충분한 양의 금속이온과 환원제가 공급된다면 동일한 도금용액의 양을 사용한 전기도금 대비 10 ~ 30배의 처리가 가능하여, 다량의 인쇄회로 나노섬유웹을 보다 신속히 제조할 수 있어 이와 관련된 공정상의 단순화에 현저히 기여할 수 있으며, 폐기되는 재료의 양이 줄어들어 친환경적이며 원가 절감에 장점이 있을 수 있다.Third, the circuit pattern portion can be simultaneously formed on a large amount of nanofiber web through the electroless plating method, thereby achieving the effect of process simplification and cost reduction. In other words, if a sufficient amount of metal ions and a reducing agent are supplied, 10 to 30 times of treatment is possible compared to electroplating using the same amount of plating solution, and thus a large amount of printed circuit nanofiber web can be manufactured more quickly. It can contribute significantly to the simplification and can be environmentally friendly and cost-effective because of the reduced amount of material disposed of.
네 번째, 상술한 것과 같이 무전해도금법은 도금용액에 침지시켜 산화환원 반응을 이용하기 때문에, 나노섬유웹과 같이 유연한 기재 표면 외력을 가할 필요가 없고, 특수한 처리 없이도 기재 표면을 손상시키지 않고 회로패턴을 도금시킬 수 있는 장점이 있다.Fourth, as described above, the electroless plating method uses a redox reaction by immersing in a plating solution, so that it is not necessary to apply a flexible substrate surface external force like a nanofiber web, and does not damage the substrate surface without special treatment. There is an advantage that can be plated.
이때, 본 발명에 따른 인쇄회로 나노섬유웹을 제조하기 위해서는 나노섬유웹 상에 회로패턴부가 형성될 부분을 제외한 나머지 면을 마스킹하는 단계를 수행할 수 있다.At this time, in order to manufacture a printed circuit nanofiber web according to the present invention may be performed to mask the remaining surface except for the portion where the circuit pattern portion is to be formed on the nanofiber web.
상기 마스킹은 나노섬유웹의 특정 부분에만 회로패턴부를 형성시키기 위한 것으로 나노섬유웹의 물성에 영향을 미치지 않는 범위에서 공지의 무전해 도금용 마스킹 공정이 제한 없이 사용될 수 있다. 일 예로, 테이프 형태의 마스킹제를 회로패턴부가 형성될 부분을 제외한 나노섬유웹 전면에 접착시킴으로써, 회로패턴부가 형성되는 위치를 조절할 수 있으며, 다른 예로 액상 실리콘으로 이루어진 마스킹제를 스프레이 방식으로 도포시키는 방법을 이용할 수 있다. 또 다른 예로 나노섬유웹이 인입될 수 있는 케이스의 형태로 제작된 마스크를 통해 특정 위치에만 회로패턴부를 형성시킬 수 있다. 이후, 이와 같이 마스킹된 나노섬유웹은 후술한 도금 용액에 침지시켜 특정 부분에만 회로패턴부를 형성할 수 있다,The masking is to form a circuit pattern portion only on a specific portion of the nanofiber web, and a known masking process for electroless plating may be used without limitation in a range that does not affect the physical properties of the nanofiber web. For example, by attaching a tape-type masking agent to the entire surface of the nanofiber web except for the portion where the circuit pattern portion is to be formed, the position at which the circuit pattern portion is formed can be controlled, and in another example, a masking agent made of liquid silicon is applied by spraying. Method can be used. As another example, the circuit pattern part may be formed only at a specific position through a mask manufactured in the form of a case into which the nanofiber web may be inserted. Subsequently, the masked nanofiber web may be immersed in the plating solution described below to form a circuit pattern portion only at a specific portion.
한편, 상기 (2) 단계는, 2-1) 상기 나노섬유웹을 촉매 용액에 침지시켜 촉매화 처리하는 단계; 2-2) 촉매화 처리된 상기 나노섬유웹을 활성화시키는 단계; 및 2-3) 활성화된 상기 나노섬유웹을 무전해도금법을 통해 회로패턴부를 형성시키는 단계;를 포함할 수 있다. 이때, 상기 (2) 단계를 수행하기 전에 상기 나노섬유웹을 탈지시키거나 친수화 처리하는 단계;를 더 포함할 수 있다.On the other hand, step (2), 2-1) immersing the nanofiber web in a catalyst solution to catalyze the treatment; 2-2) activating the catalyzed nanofiber web; And 2-3) forming the circuit pattern part by electroless plating the activated nanofiber web. At this time, the step of degreasing or hydrophilizing the nanofiber web before the step (2); may further include.
상기 탈지 단계는 회로패턴부가 형성될 나노섬유웹의 표면에 존재하는 산화물이나 이물질, 특히 유지분 등을 산 또는 알칼리 계면활성제로 처리하여 세척하는 단계이다. 이때, 상기 탈지 단계를 통해 회로패턴부가 형성될 나노섬유웹의 표면이 세척되지 않는다면 이물질 또는 보이드 현상에 의하여 촉매 또는 활성 단계의 화학 반응이 저해될 수 있어 회로패턴부의 도금이 균일하게 형성되지 않을 수 있으며, 도금되더라도 회로패턴부와 나노섬유웹의 접착력이 매우 불량해져 제품 신뢰성이 크게 저하될 우려가 있다. 다만 탈지 단계에서 사용되는 산 또는 알칼리 계면활성제가 완전히 수세되지 않는다면, 이로 인한 후속 처리용액(촉매 용액 또는 활성화 용액)에 대한 오염물질로 작용할 수 있어 적정 범위의 온도와 압력을 통해 상기 계면활성제를 충분히 수세하여야 한다.The degreasing step is a step of washing an oxide or a foreign substance, particularly an oil or fat, present on the surface of the nanofiber web on which the circuit pattern part is to be formed by treating with an acid or an alkali surfactant. At this time, if the surface of the nanofiber web to be formed through the degreasing step is not washed, the chemical reaction of the catalyst or the active step may be inhibited by foreign substances or voids, so that the plating of the circuit pattern part may not be uniformly formed. In addition, even if plated, the adhesion between the circuit pattern portion and the nanofiber web is very poor, and there is a fear that the product reliability is greatly reduced. However, if the acid or alkali surfactants used in the degreasing step are not washed thoroughly, they can act as contaminants for subsequent treatment solutions (catalyst solutions or activating solutions), so that the surfactants can You must wash.
상기 친수화 단계는 소수성 나노섬유웹 표면을 친수성으로 전환하는 동시에 카르복실기, 아민기, 하이드록실기 등의 관능기를 나노섬유웹 표면에 도입하여 금속이온의 흡착을 용이하게 하고 나노섬유웹 표면에 미세한 공동을 형성시켜 표면 거칠기를 높여 석출되는 금속피막과 나노섬유웹 표면과의 접착력을 향상시키는 단계이다. 상기 친수화 단계는 알칼리금속 수산화물이나 질소화합물을 계면활성제와 혼합하여 수행할 수 있으며, 상기 수산화물은 수산화나트륨(NaOH), 수산화칼륨(KOH) 등이 사용될 수 있으며, 상기 질소화합물은 암모늄염 또는 아민화합물 등을 포함할 수 있다. 상기 암모늄염은 예를 들어, 수산화암모늄, 염화암모늄, 황산암모늄, 탄산암모늄 또는 트리에틸암모늄염, 테트라에틸암모늄염, 트리메틸암모늄염, 테트라메틸암모늄염, 트리플루오르암모늄염, 테트라플루오르암모늄염 등의 알킬기나 아릴기가 치환된 암모늄염 등이 사용될 수 있으며, 상기 아민화합물은 예를들어, 메틸아민, 에틸아민, 디메틸아민, 디에틸아민, 트리메틸아민, 에틸렌디아민, 디에틸렌트리아민 등의 지방족 아민화합물, 또는 우레아 및 히드라진 유도체 등이 사용될 수 있다. 상기 계면활성제는 알킬술폰산나트륨(SAS), 알킬황산에스테르나트륨(AS), 올레핀술폰산나트륨(AOS), 알킬 베젠술폰산염(LAS) 등의 음이온 계면활성제, 양이온 계면활성제, 또는 중성 계면활성제 등을 사용할 수 있다. 이때, 상기 화합물들이 포함된 친수화 용액에 20 ~ 100℃에서 1 ~ 20분 동안 나노섬유웹을 침적하여 친수화 단계를 수행한다.The hydrophilization step converts the surface of the hydrophobic nanofiber web into hydrophilic and simultaneously introduces functional groups such as carboxyl groups, amine groups and hydroxyl groups to the nanofiber web surface to facilitate the adsorption of metal ions and fine cavities on the nanofiber web surface. It is a step of improving the adhesion between the surface of the deposited metal film and the nanofiber web by increasing the surface roughness. The hydrophilization step may be performed by mixing an alkali metal hydroxide or nitrogen compound with a surfactant, the hydroxide may be used sodium hydroxide (NaOH), potassium hydroxide (KOH), etc., the nitrogen compound is an ammonium salt or an amine compound And the like. The ammonium salt is, for example, ammonium salt substituted with an alkyl group or an aryl group, such as ammonium hydroxide, ammonium chloride, ammonium sulfate, ammonium carbonate or triethylammonium salt, tetraethylammonium salt, trimethylammonium salt, tetramethylammonium salt, trifluoroammonium salt or tetrafluoroammonium salt. The amine compound may be, for example, aliphatic amine compounds such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, ethylenediamine, diethylenetriamine, or urea and hydrazine derivatives. Can be used. The surfactant may be anionic surfactants such as sodium alkyl sulfonate (SAS), sodium sodium sulfate ester (AS), sodium olefin sulfonate (AOS), alkyl bezen sulfonate (LAS), cationic surfactants, or neutral surfactants. Can be. At this time, the hydrophilization step is performed by depositing the nanofiber web for 1 to 20 minutes at 20 ~ 100 ℃ in a hydrophilization solution containing the compounds.
그리고, 상기 2-1) 단계는 탈지 및 친수화 단계를 거친 나노섬유웹 표면에 촉매입자를 석출시켜 도금이 용이하도록 하기 위해 촉매화(Catalyzing)처리를 수행하는 단계이다.In the step 2-1), the catalyst particles are deposited on the surface of the nanofiber web subjected to the degreasing and hydrophilization to carry out the catalyzing treatment to facilitate plating.
상기 촉매용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe의 염으로 이루어진 군에서 선택되는 어느 하나 이상의 화합물을 포함하며, 바람직하게는 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe의 염으로 이루어진 콜로이드 용액 또는 귀금속 착이온 등으로 사용할 수 있다. 일 예로 상기 콜로이드 용액은 초순수 1리터당 염산 50 ~ 250㎖과, 염화나트륨 혹은 염화칼륨 50 ~ 300g, 염화주석(SnCl2) 5 ~ 60g, 염화팔라듐(PdCl2) 0.1 ~ 5g 로 이루어진 군에서 선택된 1종 이상의 염이 포함된 용액을 사용할 수 있다.The catalyst solution includes at least one compound selected from the group consisting of salts of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, preferably Ti, Sn, Au, It can be used as a colloidal solution consisting of salts of Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, or a noble metal complex ion. For example, the colloidal solution is at least one selected from the group consisting of 50 to 250 ml of hydrochloric acid per liter of ultrapure water, 50 to 300 g of sodium chloride or potassium chloride, 5 to 60 g of tin chloride (SnCl 2 ), and 0.1 to 5 g of palladium chloride (PdCl 2 ). Solutions containing salts can be used.
이때, 상기 2-1) 수행 전, 상기 촉매 입자의 흡착 효율을 향상시키기 위하여 예비 촉매처리단계로써, 사전침적(pre-dip)공정을 수행할 수 있으며 상기 사전침적 공정은 촉매처리에 앞서 낮은 온도의 촉매용액에 나노섬유웹을 침지시켜 촉매처리 단계에서 사용되는 촉매용액이 오염되거나 농도가 변화하는 것을 방지하기 위한 처리단계이다.At this time, before performing the 2-1), as a pre-catalyst treatment step to improve the adsorption efficiency of the catalyst particles, a pre-dip process may be performed, and the pre-deposition process is performed at a low temperature prior to the catalyst treatment. It is a treatment step for preventing the contamination of the catalyst solution used in the catalyst treatment step or the concentration change by immersing the nanofiber web in the catalyst solution of.
다음, 촉매화 처리된 상기 나노섬유웹을 활성화시키는 2-2) 단계를 수행한다.Next, step 2-2) of activating the catalyzed nanofiber web is performed.
상기 활성화 단계는 촉매화 단계 이후, 흡착된 금속입자의 활성도와 무전해도금용액의 석출거동을 향상시키기 위한 단계이다. 이러한 활성화 단계를 통해 콜로이드 입자를 둘러싸고 있는 금속입자를 제거하고 흡착된 촉매만 남도록 하여 무전해금속피막의 석출 더욱더 용이하게 할 수 있다. 일 예로 상기 활성화 공정은 증류수 및 황산의 혼합용액에서 30초 ~ 5분간, 바람직하게는 30초 ~ 3분간 침적시키는 단계일 수 있다.The activation step is a step for improving the activity of the adsorbed metal particles and the precipitation behavior of the electroless plating solution after the catalysis step. Through this activation step, the metal particles surrounding the colloidal particles are removed and only the adsorbed catalyst remains, thereby making the deposition of the electroless metal film even easier. For example, the activation process may be a step of depositing 30 seconds to 5 minutes, preferably 30 seconds to 3 minutes in a mixed solution of distilled water and sulfuric acid.
다음, 활성화된 상기 나노섬유웹에 무전해도금법을 통해 회로패턴부를 형성시키는 2-3) 단계를 수행한다.Next, steps 2-3) are performed on the activated nanofiber web to form a circuit pattern part by electroless plating.
상기 무전해도금법은 일반적으로 환원도금법과 치환도금법으로 구분될 수 있으며 환원도금법은 환원반응을 통하여 금속이 석출되어 기재표면에 도금되는 방법이고, 치환도금법은 금속의 환원력 차이에 의하여 환원력이 상대적으로 큰 금속이 석출되어 도금되는 방법이며, 상기 2-3) 단계는 본 발명의 일 예에 따라 치환도금법을 이용할 수 있다.The electroless plating method may be generally divided into reduction plating method and substitution plating method, and reduction plating method is a method in which metal is precipitated and plated on the surface of a substrate through reduction reaction, and substitution plating method has a relatively large reducing power due to a difference in reducing power of metal. A metal is deposited and plated, and the step 2-3) may use a substitution plating method according to an embodiment of the present invention.
상기 치환도금법은 상대적으로 환원력이 작은 1차 도금용액에 나노섬유웹을 침지시키고, 이후 상대적으로 환원력이 강한 2차 도금용액에 나노섬유웹을 침지시켜 2차 도금용액의 금속을 석출시켜 도금하는 방법으로, 상기 1차 및 2차 도금용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe로 이루어진 군에서 선택되는 금속을 포함할 수 있고, 이와 같은 치환도금법은 40 ~ 80℃에서 0.5분 ~ 10분 동안, 바람직하게는 45 ~ 75℃에서 1분 ~ 8분 동안 침지시킴으로써 최종적으로 구리이온이 도금된 인쇄회로 나노섬유웹을 얻을 수 있다.In the substitution plating method, the nanofiber web is immersed in the primary plating solution having a relatively low reducing power, and the nanofiber web is immersed in the secondary plating solution having a relatively reducing power, thereby depositing and plating the metal of the secondary plating solution. In addition, the primary and secondary plating solution may include a metal selected from the group consisting of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe, such substitution plating method A copper ion plated printed circuit nanofibrous web can be finally obtained by immersing at 40 to 80 ° C. for 0.5 to 10 minutes, preferably at 45 to 75 ° C. for 1 minute to 8 minutes.
상기 (2) 단계를 통해 인쇄회로 나노섬유웹에 형성된 회로패턴부는 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하여 형성된다. 즉 도 3 및 도 4를 참조하면, 회로패턴부가 형성된 나노섬유웹의 소정의 영역(A영역)의 나노섬유는 회로패턴부가 형성되지 않은 나노섬유웹의 영역(B영역)와 달리, 나노섬유 외부면에 회로패턴부가 피복된 시스/코어 형태와 같은 나노섬유로 이루어질 수 있다.The circuit pattern part formed on the printed circuit nanofiber web through step (2) is formed by covering the outer surface of the nanofiber included in a predetermined area on the nanofiber web. That is, referring to FIGS. 3 and 4, the nanofibers in the predetermined region (region A) of the nanofiber web on which the circuit pattern portion is formed are different from the outer region of the nanofiber, unlike the region (region B) of the nanofiber web on which the circuit pattern portion is not formed. It may be made of nanofibers, such as the sheath / core form coated on the circuit pattern portion.
또한, 상기 회로패턴부는 두께가 0.1 ~ 10 ㎛, 바람직하게는 두께가 0.2 ~ 3㎛일 수 있다. 만일 상기 회로패턴부의 두께가 0.1 ㎛ 미만이면 박형화에 유리할 수 있으나, 회로패턴부의 두께가 너무 얇아서 회로패턴부를 통한 전기적 특성에 대한 안정성이 저하될 우려가 있고, 회로패턴부와 나노섬유웹의 접착력이 저하되어 제품 내구성 및 신뢰성에 문제가 발생할 수 있으며, 인쇄회로 나노섬유웹의 기공도가 높아짐에 따라 내구성 및 기계적 물성이 저하될 수 있다. 또한, 만일 회로패턴부의 두께가 10㎛ 초과하면 회로패턴부의 중량으로 인해 나노섬유웹의 지지기능이 저하되어 기계적 물성이 저하될 수 있고, 소형 전자제품의 용도로써 경량화 및 박형화면에서 불리할 수 있으며, 인쇄회로 나노섬유웹의 기공도가 낮아짐에 따라 신축성이 저하되는 문제가 있을 수 있고, 내구성 및 공정성이 저하될 수 있다.In addition, the circuit pattern portion may have a thickness of 0.1 to 10 μm, preferably 0.2 to 3 μm. If the thickness of the circuit pattern portion is less than 0.1 ㎛ may be advantageous in thinning, but because the thickness of the circuit pattern portion is too thin, there is a fear that the stability of the electrical characteristics through the circuit pattern portion is lowered, the adhesion between the circuit pattern portion and the nanofiber web The degradation may cause problems in product durability and reliability, and as the porosity of the printed circuit nanofiber web increases, durability and mechanical properties may decrease. In addition, if the thickness of the circuit pattern portion exceeds 10㎛ the support function of the nanofiber web due to the weight of the circuit pattern portion may degrade the mechanical properties, may be disadvantageous in light weight and thin screen as a use of small electronic products. As the porosity of the printed circuit nanofiber web is lowered, there may be a problem that the elasticity is lowered, and durability and processability may be lowered.
한편, 본 발명의 일 실시예에 따른 나노섬유웹은 회로패턴부에 의해 형성되는 상부영역의 제1패턴과 하부영역의 제2패턴을 각각 포함할 수 있고, 상기 제1패턴과 제2패턴은 서로 동일한 패턴으로 형성될 수 있다. 이 경우, 나노섬유웹의 두께를 조절하여 한번의 침지를 통해 동일한 회로패턴을 형성할 수 있어 공정 단순화 및 경제성 면에서의 장점이 있다. 또한, 이와 반대로 제1패턴부 및 제2패턴부는 서로 다른 회로패턴으로 구현될 수 있으며, 본 발명에 따른 인쇄회로 나노섬유웹의 목적 및 용도를 고려하여 적절히 선택될 수 있으므로 회로패턴부의 형상 및 크기는 특별히 제한하지 않는다.On the other hand, the nanofiber web according to an embodiment of the present invention may include a first pattern of the upper region and a second pattern of the lower region formed by the circuit pattern portion, respectively, the first pattern and the second pattern It may be formed in the same pattern with each other. In this case, the same circuit pattern can be formed through one immersion by adjusting the thickness of the nanofiber web, which has advantages in process simplification and economics. In addition, on the contrary, the first pattern portion and the second pattern portion may be embodied in different circuit patterns, and may be appropriately selected in consideration of the purpose and use of the printed circuit nanofiber web according to the present invention. Is not particularly limited.
한편, 상기 인쇄회로 나노섬유웹은 상기 (2) 단계에서 무전해도금법을 사용하는 대신에 인쇄전자 기법을 통해 나노섬유웹의 적어도 일면에 회로패턴층을 형성할 수 있다. 이 경우, 목적하는 회로패턴 부분만을 기판이나 필름 등에 전도성 전자잉크로 인쇄하여 제조하기 때문에 두 단계의 공정으로 회로패턴을 인쇄할 수 있어 공정 단순화에 크게 기여할 수 있으며, 회로 패턴 형성의 정확성이 향상되고, 낭비되는 재료가 거의 없어 제조 단가를 크게 낮출 수 있다.On the other hand, the printed circuit nanofiber web may form a circuit pattern layer on at least one surface of the nanofiber web through a printed electronic technique instead of using the electroless plating method in the step (2). In this case, since only the desired circuit pattern portion is manufactured by printing with conductive electronic ink on a substrate or film, the circuit pattern can be printed in a two-step process, which greatly contributes to the simplification of the process, and improves the accuracy of the circuit pattern formation. Therefore, there is almost no wasted material, and the manufacturing cost can be greatly reduced.
이때, 상기 인쇄전자 기법은 당업계에서 통상적으로 사용할 수 있는 인쇄전자 기법일 수 있고, 바람직하게는 잉크젯프린팅(Inkjet Printing) 및 플렉소인쇄법(Flexography) 중 어느 하나의 방법으로 수행될 수 있다. 다만 본 발명에서의 인쇄전자 기법은 상기 언급된 방법에 한정되는 것은 아니며, 인쇄전자 기법으로 이용될 수 있는 모든 방법을 포함할 수 있다.In this case, the printed electronic technique may be a printed electronic technique commonly used in the art, and preferably, may be performed by any one method of inkjet printing and flexography. However, the printed electronic technique in the present invention is not limited to the above-mentioned method, and may include all methods that may be used as the printed electronic technique.
이때, 상기 잉크젯프린팅(Inkjet Printing) 방법은 헤드로부터 미세한 크기의 전도성 잉크 방울(이하, 액적이라 한다)을 토출하여 목적하는 기재에 충돌시켜 회로 패턴을 형성하는 방식이며, 액적 토출 방식에 따라 연속적으로 액적을 토출시키는 컨티뉴어스(Continuous) 방식과 선택적으로 액적을 토출시키는 드롭 온 디맨드(Drop On Demand) 방식으로 분류할 수 있다. 이때, 컨티뉴어스 방식은 일반적으로 대형의 장치가 요구되고 저해상도의 패터닝(Patterning)에 이용됨에 반해, 드롭 온 디맨드 방식은 고해상도의 패터닝이 필요한 경우에 사용되는 특징이 있다.At this time, the inkjet printing method is a method of forming a circuit pattern by ejecting conductive ink droplets (hereinafter, referred to as droplets) having a small size from a head and colliding with a target substrate, and continuously according to the droplet ejection method. It may be classified into a continuous method of discharging droplets and a drop on demand method of discharging droplets. In this case, the continuous method generally requires a large device and is used for low resolution patterning, whereas the drop on demand method is used when high resolution patterning is required.
또한, 상기 드롭 온 디맨드(Drop On Demand) 방식은 다시 압전소자를 이용해 잉크에 압력을 인가하여 액적을 토출시키는 피에조(Piezo) 방식 및 잉크에 열을 가해 순간적으로 기포를 발생시킨 후 기포의 압력에 의해 액적을 토출시키는 버블젯(Bubblejet) 방식으로 분류할 수 있다. 상기 피에조(Piezo) 방식의 경우 잉크에 열을 가하지 않기 때문에 헤드 수명이 비교적 길다는 점 및 잉크의 선택에 있어 열변성을 고려해야 하는 제한이 없다는 점은 유리하나 고해상도의 패터닝을 위해서는 헤드의 생산비용이 상승한다는 점에서 불리할 수 있다.In addition, the Drop On Demand method uses a piezo method that applies pressure to ink again using a piezoelectric element and heats the ink to generate air bubbles and then to the pressure of the bubbles. Can be classified into a bubble jet method for discharging droplets. In the case of the Piezo method, it is advantageous that the head life is relatively long because no heat is applied to the ink, and there is no restriction to consider thermal denaturation in the selection of the ink, but the production cost of the head is high for high resolution patterning. It can be disadvantageous in that it rises.
상기 플렉소 인쇄법(Flexography) 방법은 균일한 그레이팅(Grating)을 갖는 아니록스 롤러(Anilox Roller) 위에 전도성 잉크를 도포하고, 닥터 블레이드를 통해 균일하게 펼친 후, 상기 아니록스 롤러(Anilox Roller)와 인쇄롤을 접촉시켜 상기 인쇄롤의 유연성 수지판 위에 양각된 패턴으로 전도성 잉크를 전사함으로써 목적하는 기재 표면에 프린팅 하는 방식이다.The flexography method applies conductive ink on an anilox roller having a uniform grating, spreads it evenly through a doctor blade, and then the anilox roller. It is a method of printing on the surface of the desired substrate by transferring the conductive ink in a pattern embossed on the flexible resin plate of the printing roll by contacting the printing roll.
이때, 상기 인쇄전자 기법은, 나노섬유웹에 전도성 잉크를 분사하는 단계 및 분사된 전도성 잉크를 소결하여 나노섬유웹의 적어도 일면에 회로패턴층을 형성하는 단계를 포함하여 구현될 수 있다.In this case, the printed electronic technique may be implemented by spraying a conductive ink on the nanofiber web and sintering the sprayed conductive ink to form a circuit pattern layer on at least one surface of the nanofiber web.
상기 전도성 잉크를 분사하는 단계에서 상기 전도성 잉크는 금, 은, 구리, 백금, 팔라듐, 니켈, 알루미늄 및 카본 입자 중 적어도 하나 이상의 전도성 입자를 포함할 수 있으며, 도전성 및 내화학성을 고려하면 금, 은, 백금이 바람직하고, 비용 및 후술할 소결 온도를 고려하면 은이 보다 바람직할 수 있다. 다만, 상기 전도성 잉크에 포함되는 전도성 입자는 상기 언급된 금속에 한정되지 아니하며, 전도성 잉크의 재료로 사용될 수 있는 모든 금속 또는 비금속을 포함한다. 예를 들어 포름산 금, 포름산 은, 포름산 구리, 포름산 백금, 포름산 팔라듐, 포름산니켈, 포름산 알루미늄, 아세트산 금, 아세트산 은, 아세트산 구리, 아세트산 백금, 아세트산 팔라듐, 아세트산 니켈, 아세트산 알루미늄, 옥살산 금, 옥살산 은, 옥살산 구리, 옥살산 백금, 옥살산 팔라듐, 옥살산 니켈, 옥살산 알루미늄, 말론산 금, 말론산 은, 말론산 구리, 말론산 백금, 말론산 팔라듐, 말론산 니켈, 말론산 알루미늄, 프탈산 금, 프탈산 은, 프탈산 구리, 프탈산 백금, 프탈산 팔라듐, 프탈산 니켈, 프탈산 알루미늄 등을 상기 전도성 잉크의 전도성 입자로써 포함할 수 있다. 이떄 상기 전도성 입자는 나노 또는 마이크로 스케일 수 있으며, 회로패턴층의 물성에 따라 전도성 입자의 종류와 전도성 잉크의 함유되는 비율을 적절히 선택 가능함에 따라 특별히 한정하지 않는다.In the spraying of the conductive ink, the conductive ink may include at least one conductive particle among gold, silver, copper, platinum, palladium, nickel, aluminum, and carbon particles, and considering the conductivity and chemical resistance, gold, silver Platinum is preferable, and silver may be more preferable in consideration of cost and sintering temperature described later. However, the conductive particles included in the conductive ink are not limited to the above-mentioned metals, and include all metals or nonmetals that can be used as the material of the conductive ink. For example, gold formate, silver formate, copper formate, platinum formate, palladium formate, nickel formate, aluminum formate, gold acetate, silver acetate, copper acetate, platinum acetate, palladium acetate, nickel acetate, aluminum acetate, gold oxalate, silver oxalate Copper oxalate, platinum oxalate, palladium oxalate, nickel oxalate, aluminum oxalate, gold malonate, silver malonate, copper malonate, platinum malonate, palladium palladium, nickel malonate, aluminum malonate, gold phthalate, silver phthalate, Copper phthalate, platinum phthalate, palladium phthalate, nickel phthalate, aluminum phthalate, and the like may be included as the conductive particles of the conductive ink. The conductive particles may be nano or micro scale, and the type of the conductive particles and the content of the conductive ink may be appropriately selected according to the physical properties of the circuit pattern layer.
또한 상기 전도성 잉크는 상기 전도성 입자의 균일한 분산을 위하여 용매 및 바인더를 더 포함할 수 있으며 목적하는 용도 및 필요에 따라, 본 발명의 효과에 영향을 주지 않는 범위에서 인쇄전자에 적용되는 첨가제를 함유시키는 것이 가능하다. 일 예로 점도 조제제, 도전 조제, 초킹(Chalking) 방지제, 산화 방지제, pH 조제제, 건조 방지제, 밀착 부여제, 방부제, 소포제, 레벨링제(leveling agent), 계면활성제 등을 예시할 수 있으며, 바인더를 첨가하는 경우 나노섬유웹과의 접착성이 향상되어, 전도성 잉크의 균일한 분산을 유도할 수 있다. 이와 같이 추가적인 첨가제들의 조성과 조성비는 후술할 소결 과정을 통해 전부 증발하여 균일한 회로패턴층을 형성할 수 있도록, 회로패턴층의 물성을 고려하여 적절히 선택될 수 있다.In addition, the conductive ink may further include a solvent and a binder for uniform dispersion of the conductive particles and, depending on the intended use and need, contains an additive applied to the printed electronics in a range that does not affect the effect of the present invention. It is possible to let. As an example, a viscosity aid, a conductive aid, a chalking inhibitor, an antioxidant, a pH aid, a drying inhibitor, an adhesion agent, a preservative, an antifoaming agent, a leveling agent, a surfactant, and the like can be exemplified. When added to improve the adhesion with the nanofiber web, it can induce a uniform dispersion of the conductive ink. As such, the composition and the ratio of the additional additives may be appropriately selected in consideration of the physical properties of the circuit pattern layer so as to form a uniform circuit pattern layer by evaporating through the sintering process to be described later.
한편 상기 전도성 잉크에 포함되는 전도성 입자를 상술한 것과 같이 용매(solvent)에 분산시켜 제작할 수 있는데, 분산 초기 전도성 입자는 매우 불안정한 상태로 분산되어 있기 때문에, 전도성 입자들이 다시 응집되는 현상이 발생할 수 있다. 특히 본 발명과 같이 전도성 입자를 나노 사이즈로 사용하는 경우 이러한 응집에 의해, 인쇄 공정을 통해 회로패턴 형성 시 회로패턴층의 균일성(uniformity) 및 전기전도 특성이 나빠지는 전기적 특성 저하가 발생될 수 있다.Meanwhile, the conductive particles included in the conductive ink may be prepared by dispersing them in a solvent as described above. Since the conductive particles are dispersed in a very unstable state, the conductive particles may aggregate again. . In particular, when the conductive particles are used in the nano-size as in the present invention, such agglomeration may cause deterioration of electrical properties, which may result in poor uniformity and electrical conductivity of the circuit pattern layer when the circuit pattern is formed through the printing process. have.
따라서 후술하는 회로패턴층을 형성하는 단계에서 소결을 수행하여 특별히 분산을 제어하는 분산제 등을 사용하지 않고 균일한 회로패턴층을 형성시킬 수 있다.Therefore, sintering may be performed in the step of forming a circuit pattern layer to be described later to form a uniform circuit pattern layer without using a dispersant that specifically controls dispersion.
다음, 분사된 전도성 잉크를 소결하여 나노섬유웹의 적어도 일면에 회로패턴층을 형성하는 단계를 수행한다.Next, the sprayed conductive ink is sintered to form a circuit pattern layer on at least one surface of the nanofiber web.
상기 회로패턴층을 형성하는 단계는 전도성 잉크를 고화시켜 회로패턴층을 형성시키는 단계이며, 상술한 것과 같이 추가적 효과로써, 전도성 잉크의 분산 안정성 및 균일도를 향상시켜 보다 균일한 회로패턴층이 형성시키는 단계이다.The forming of the circuit pattern layer is a step of forming a circuit pattern layer by solidifying the conductive ink, and as an additional effect as described above, improves dispersion stability and uniformity of the conductive ink to form a more uniform circuit pattern layer. Step.
소결(sintering)이란 분체가 외부로부터 강한 에너지를 받을 경우 분체 입자 간에 결합이 일어나서 응고하는 현상을 의미하며, 상기 금속 입자들로 구성된 전도성 잉크의 경우, 소결 과정을 거치면 단순히 입자들이 서로 결합하여 입자 사이즈가 커져 이상적으로 공극이 존재하지 않는 박막 형태로 변할 뿐만 아니라 분산안정성을 향상시키기 위해 금속 입자의 표면에 추가적으로 포함된 첨가제 등의 물질이 열분해 또는 휘발되어 사라지게 되므로, 전도도 특성을 극대화시킬 수 있다.Sintering refers to a phenomenon in which a powder is bound and solidified when the powder receives strong energy from the outside. In the case of the conductive ink composed of the metal particles, when the powder is sintered, the particles simply bind to each other to form a particle size. Is not only ideally changed into a thin film form in which no pores exist, but also materials such as additives, which are additionally included on the surface of the metal particles, disappear due to pyrolysis or volatilization to improve dispersion stability, thereby maximizing conductivity characteristics.
본 발명의 일 예에 따른 소결 처리 방식은 기판에 인쇄된 잉크를 오븐(oven)이나 노(furnace)를 이용하여 열처리를 수행할 수 있다. 다만 이에 제한되지 않으며, 회로패턴층이 형성되는 나노섬유웹의 물성에 영향을 주지 않는 범위에서 공지된 다양한 소결 처리 방식을 수행할 수 있다.In the sintering treatment method according to an embodiment of the present invention, the ink printed on the substrate may be heat treated using an oven or a furnace. However, the present invention is not limited thereto, and various known sintering methods may be performed in a range that does not affect the physical properties of the nanofiber web on which the circuit pattern layer is formed.
한편, 본 발명에 따른 인쇄회로 나노섬유웹을 구현하는 제조방법은 무전해도금법을 이용하여 유연한 나노섬유웹 상에 회로패턴부가 치밀하고 균일한 두께를 가지도록 형성할 수 있는 동시에 다수의 기공을 가지는 나노섬유웹을 통해 방수성과 통기성 특성을 만족함에 따라서 바이오패치 등의 의료기기, 스마트기기 등의 전자기기를 포함하여 각종 미래산업분야에서 다양하게 응용될 수 있다.On the other hand, the manufacturing method for implementing a printed circuit nanofiber web according to the present invention can be formed to have a dense and uniform thickness of the circuit pattern portion on the flexible nanofiber web using an electroless plating method and at the same time have a number of pores As it meets the waterproof and breathable characteristics through the nanofiber web, it can be variously applied in various future industrial fields including electronic devices such as medical devices and smart devices such as biopatches.
또한, 본 발명은 도 3에 도시된 것과 같이, 다수 개의 나노섬유(110)를 포함하는 나노섬유웹(100) 및 상기 나노섬유웹(100) 상 소정의 영역 내에 포함된 나노섬유(110)의 외부면을 피복하여 형성되는 회로패턴부(120)를 포함하는 인쇄회로 나노섬유웹을 구현하며, 상기 소정의 영역은 나노섬유웹(100) 상에 회로패턴부(120)가 형성될 영역(A)을 의미한다. 기타 인쇄회로 나노섬유웹에 대한 설명은 상술한 제조방법 (2) 단계에 따른 설명과 동일하므로 생략하기로 한다.In addition, the present invention, as shown in Figure 3, of the nanofiber web 100 including a plurality of nanofibers 110 and the nanofibers 110 included in a predetermined region on the nanofiber web 100 A printed circuit nanofiber web including a circuit pattern part 120 formed by covering an outer surface is implemented, and the predetermined area is an area A in which the circuit pattern part 120 is to be formed on the nanofiber web 100. ). The description of the other printed circuit nanofiber web is the same as the description according to the manufacturing method (2) described above will be omitted.
또한, 도 8 및 도 9을 참조하면, 유연한 소재의 나노섬유웹 상에 다양한 형태의 회로패턴부를 형성할 수 있다. 즉, 본 발명에 따른 인쇄회로 나노섬유웹은 종래 연성인쇄회로기판보다 현저히 향상된 가요성 및 복원력을 가지고 있을 뿐만 아니라 우수한 유연성 및 신축성을 보유함에 따라 최근 각광받고 있는 의료산업 분야의 바이오패치로의 활용은 물론, 실질적으로 신체 어느 부위에나 부착할 수 있는 다양한 센서의 형태로도 제작이 가능하여 향후 사물인터넷을 비롯한 전자기기와 관련된 다양한 산업분야로의 활용도를 제고하여 관련 산업분야 발전을 촉진시킬 수 있다.8 and 9, various types of circuit pattern parts may be formed on the nanofiber web made of a flexible material. That is, the printed circuit nanofiber web according to the present invention not only has significantly improved flexibility and resilience than the conventional flexible printed circuit board, but also has excellent flexibility and elasticity, and thus is utilized as a biopatch in the medical industry which is recently attracting attention. In addition, it can be manufactured in the form of various sensors that can be attached to virtually any part of the body, thereby promoting the development of related industries by improving the utilization in various industrial fields related to electronic devices including the Internet of Things in the future. .
또한 본 발명은 상술한 인쇄회로 나노섬유웹 및 상기 인쇄회로 나노섬유웹에 실장된 적어도 하나 이상의 전자부품을 포함하는 전자장치를 구현한다.In addition, the present invention implements an electronic device including the above-described printed circuit nanofiber web and at least one electronic component mounted on the printed circuit nanofiber web.
상기 전자부품은 목적하는 다양한 산업에 따라 적절히 선택될 수 있으며, 일예로 상기 전자 부품은 사용자의 신체 상태를 검출하기 위한 바이오 센서와 주변환경을 감지하기 위한 환경감지센서 중 적어도 하나를 포함하는 센서유닛, 근거리 무선 통신에 사용되는 근거리 통신 모듈, 무선 통신에 사용되는 안테나 패턴 및 신호처리 기능을 수행하기 위한 제어유닛을 포함하는 전자 기기일 수 있다.The electronic component may be appropriately selected according to various industries desired. For example, the electronic component may include a sensor unit including at least one of a biosensor for detecting a user's physical condition and an environmental sensor for sensing a surrounding environment. The electronic device may include a short range communication module used for short range wireless communication, an antenna pattern used for wireless communication, and a control unit for performing a signal processing function.
하기의 실시예를 통하여 본 발명을 더욱 구체적으로 설명하기로 하지만, 하기 실시예가 본 발명의 범위를 제한하는 것은 아니며, 이는 본 발명의 이해를 돕기 위한 것으로 해석되어야 할 것이다.Although the present invention will be described in more detail with reference to the following examples, the following examples are not intended to limit the scope of the present invention, which will be construed as to aid the understanding of the present invention.
<실시예 1><Example 1>
먼저, 방사용액을 제조하기 위하여 섬유형성성분으로 폴리비닐리덴플루오라이드 100 중량부에 대하여 폴리우레탄을 30 중량부 혼합하고, 상기 섬유형성성분 15g을 디메틸아세트아마이드와 아세톤의 중량비를 70:30으로 하여 85g에 80℃의 온도로 6시간 마그네틱바를 사용하여 용해시켜 혼합용액을 제조했다. 상기 방사용액을 전기방사장치의 용액탱크에 투입하고, 15㎕/min/hole의 속도로 토출하였다. 이때 방사 구간의 온도는 30℃, 습도는 50%를 유지하고, 콜렉터와 방사노즐팁 간 거리를 20㎝하고 고전압 발생기를 사용하여 방사 노즐 팩(Spin Nozzle Pack)에 40kV 이상의 전압을 부여함과 동시에 방사 팩 노즐 당 0.03MPa의 에어압력을 부여하여 PVDF/PU 복합 나노섬유로 형성된 섬유웹을 제조하였다. 다음으로 상기 섬유웹에 잔존하는 용매, 수분을 건조시키기 위해 140℃ 이상의 온도 및 1kgf/㎠로 열과 압력을 가해 캘린더링 공정을 실시하였다. 이때, 제조된 나노섬유웹은 두께가 20㎛이고, 기공도가 55%였다.First, to prepare a spinning solution, 30 parts by weight of polyurethane is mixed with respect to 100 parts by weight of polyvinylidene fluoride as a fiber forming component, and the weight ratio of dimethylacetamide and acetone is 15:30 of the fiber forming component. A mixed solution was prepared by dissolving 85 g at 80 ° C. using a magnetic bar for 6 hours. The spinning solution was put into a solution tank of an electrospinning apparatus and discharged at a rate of 15 µl / min / hole. At this time, the temperature of the spinning section is 30 ℃, the humidity is 50%, the distance between the collector and the spinning nozzle tip is 20cm, and a voltage of more than 40kV is applied to the spinning nozzle pack using a high voltage generator. A fiber web formed of PVDF / PU composite nanofibers was prepared by imparting an air pressure of 0.03 MPa per spin pack nozzle. Next, a calendering process was performed by applying heat and pressure at a temperature of 140 ° C. or higher and 1 kgf / cm 2 to dry the solvent and moisture remaining in the fibrous web. At this time, the prepared nanofiber web has a thickness of 20㎛, porosity was 55%.
다음으로, 패턴을 형성할 마스크 제조를 위해 실리콘 점착성분이 포함된 PET 필름을 패턴 금형에 따라 타발 공정을 통하여 마스크를 형성한다. 제조한 PET 마스크는 제조한 나노섬유웹의 두 면에 패턴만 노출되도록 마주보게 부착하여 마스킹된 나노섬유웹을 준비한다.Next, in order to manufacture a mask to form a pattern, a PET film containing a silicone adhesive component is formed through a punching process according to a pattern mold. The prepared PET mask is attached to face two surfaces of the prepared nanofiber web so that only the pattern is exposed to prepare a masked nanofiber web.
다음으로, 마스킹된 나노섬유웹에 니켈/구리인 금속쉘부를 형성시켰다. 구체적으로 나노섬유웹에 니켈/구리 무전해도금을 실시하였고, 이를 위해 나노섬유웹을 60℃의 탈지용액(ATS condiclean 10%, 순수)에 30초간 침지 뒤 순수로 세정하고, 다시 60℃의 에칭용액(5M NaOH, 순수)에 1분간 침지 뒤 순수로 세정하였다. 이후 세정한 나노섬유웹을 상온의 촉매용액(Pd 0.9%, HCl 20%, 순수)에 3분간 침지 뒤 순수로 세정했다. 이후 나노섬유웹을 촉매활성을 위한 50℃의 황산용액(H2SO4 85ml/L, 순수)에 30초간 침지 뒤 순수로 세정하고 난 뒤 나노섬유웹을 60℃의 니켈이온용액에 30초간 침지 뒤 순수로 세정하여, 두께가 0.05㎛인 니켈의 금속쉘부를 나노섬유웹의 나노섬유의 외부면에 피복시켰다. 이후 40℃의 구리이온용액에 2분간 침지 뒤 순수로 세정하여, 두께가 0.15㎛인 구리의 금속쉘부를 니켈의 금속쉘부가 형성된 나노섬유의 외부면에 피복시켰다. 금속쉘부 형성 후 마스크를 제거하여 선폭이 0.3 cm, 길이가 10 cm인 인쇄회로 나노섬유웹을 제조하였다.Next, a metal shell of nickel / copper was formed on the masked nanofiber web. Specifically, nickel / copper electroless plating was performed on the nanofiber web, and for this purpose, the nanofiber web was immersed in 60 ° C. degreasing solution (ATS condiclean 10%, pure water) for 30 seconds, washed with pure water, and then etched at 60 ° C. It was immersed in the solution (5M NaOH, pure water) for 1 minute and washed with pure water. Thereafter, the washed nanofiber web was immersed in a catalyst solution (Pd 0.9%, HCl 20%, pure water) at room temperature for 3 minutes and then washed with pure water. The nanofiber web was then immersed in 50 ° C. sulfuric acid solution (H 2 SO 4 85ml / L, pure water) for 30 seconds for catalytic activity and then rinsed with pure water. After washing with pure water, a metal shell portion of nickel having a thickness of 0.05 mu m was coated on the outer surface of the nanofibers of the nanofiber web. After immersing in a copper ion solution at 40 ℃ for 2 minutes and washed with pure water, the metal shell of copper having a thickness of 0.15㎛ was coated on the outer surface of the nanofiber formed with the metal shell of nickel. After forming the metal shell, the mask was removed to prepare a printed circuit nanofiber web having a line width of 0.3 cm and a length of 10 cm.
<실시예 2 ~ 12><Examples 2 to 12>
실시예 1과 동일하게 실시하여 제조하되, 하기 표 1 내지 표 3과 같이 나노섬유웹의 두께, 기공도, 회로패턴부의 두께 및 회로패턴부 형성방법 등을 변경하여 표 1 내지 표 3과 같은 인쇄회로 나노섬유웹을 제조하였다.Manufactured in the same manner as in Example 1, but as shown in Table 1 to Table 3 by changing the thickness of the nanofiber web, porosity, the thickness of the circuit pattern portion and the formation method of the circuit pattern portion, such as printed in Table 1 to Table 3 Circuit nanofiber webs were prepared.
<비교예 1>Comparative Example 1
실시예 1과 동일하게 실시하여 제조하되, 무전해 도금이 아닌 저항 가열식 진공증착법을 통해 니켈/구리을 증착하여 평균두께 0.2㎛가 되도록 스퍼터링을 수행하고 포토-리소그래피 공정을 진행하였다. 스핀 코터를 이용하여 포토레지스트(Photo Resist)를 표면에 코팅한 뒤 패터닝된 마스크를 이용하여 UV를 조사하였다. 이 후 현상액에 30초간 침지하여 패턴을 형성한 뒤 에칭 공정을 통해 회로패턴부를 형성하여 선폭이 0.3 cm, 길이가 10 cm인 인쇄회로 나노섬유웹을 제조하였다.Preparation was carried out in the same manner as in Example 1, but the nickel / copper was deposited by a resistive heating vacuum deposition method, not electroless plating, sputtering was carried out to an average thickness of 0.2 ㎛ and the photo-lithography process was performed. Photoresist was coated on the surface using a spin coater and then UV was irradiated using a patterned mask. Thereafter, the pattern was immersed in a developer for 30 seconds to form a pattern, and then a circuit pattern part was formed through an etching process to prepare a printed circuit nanofiber web having a line width of 0.3 cm and a length of 10 cm.
<비교예 2>Comparative Example 2
실시예 1과 동일하게 실시하여 제조하되, 나노섬유웹 대신에 폴리이미드 기판을 사용하려 인쇄회로 기판을 제조하였다.Prepared in the same manner as in Example 1, a printed circuit board was prepared to use a polyimide substrate instead of nanofiber web.
<실험예>Experimental Example
실시예 및 비교예에서 제조된 인쇄회로 나노섬유웹에 대하여 하기의 물성을 평가하여 표 1 내지 표 3에 나타내었다.The physical properties of the printed circuit nanofiber webs prepared in Examples and Comparative Examples are shown in Tables 1 to 3 below.
1. 가요성 및 복원성 평가1. Flexibility and Resilience Assessment
실시예 및 비교예에 따라 제조된 인쇄회로 나노섬유웹에 대하여 지름이 30mm 인 스테인리스 봉을 이용하여 180°굽힘 및 복원 후 초기 저항과 비교한 변동율을 측정하여 가요성 및 복원성을 평가하였다.The printed circuit nanofiber webs prepared according to the Examples and Comparative Examples were evaluated for the flexibility and the resilience by measuring the variation rate compared to the initial resistance after bending and restoring by 180 ° using a stainless steel rod having a diameter of 30 mm.
2. 신축성 평가2. Elasticity evaluation
실시예 및 비교예에 따라 제조된 인쇄회로 나노섬유웹에 대하여 지그를 이용하여 회로 패턴을 세로방향으로 1.2배 신장 후 초기 저항과 비교한 변동율을 측정하여 신축성을 평가하였다.For the printed circuit nanofiber webs prepared according to Examples and Comparative Examples, the elasticity was evaluated by measuring the variation rate compared with the initial resistance after the circuit pattern was stretched 1.2 times in the longitudinal direction using a jig.
3. 내구성 평가3. Durability Rating
실시예 및 비교예에 따라 제조된 인쇄회로 나노섬유웹에 대하여, 상기 가요성, 복원성 및 신축성 평가를 수행하는 중 아무런 문제도 발생하지 않는 경우 - ○, 회로패턴부의 박리, 크랙발생 등 어떠한 이상이라도 발생하는 경우 - ×로 하여 내구성을 평가하였다.For the printed circuit nanofiber webs prepared according to the Examples and Comparative Examples, when no problem occurs during the evaluation of the flexibility, the resilience and the elasticity-○, any abnormality such as peeling or cracking of the circuit pattern part In the case of occurrence, durability was evaluated as − ×.
4. 공정성 평가4. Fairness Assessment
실시예 및 비교예에 따라 인쇄회로 나노섬유웹을 제조하는 공정에서 아무런 이상도 없는 경우 - ○, 회로의 손상 및 불균일, 섬유웹의 박리 등 어떠한 이상이라도 발생하는 경우 - ×로 하여 공정성을 평가하였다.According to the Examples and Comparative Examples, if there is no abnormality in the process of manufacturing a printed circuit nanofiber web-○, if any abnormality such as damage and non-uniformity of the circuit or peeling of the fibrous web occurs-the fairness was evaluated as ×. .
5. 저항 측정5. Resistance measurement
실시예 및 비교예에 따라 제조된 인쇄회로 나노섬유웹에 대하여, 저항측정기(HIOKI 3540 mΩ HITESTER, HIOKI)를 통해 인쇄회로 표면의 저항을 측정하였다.For printed circuit nanofiber webs prepared according to Examples and Comparative Examples, the resistance of the surface of the printed circuit was measured through a resistance measuring instrument (HIOKI 3540 mΩ HITESTER, HIOKI).
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5
나노섬유웹Nano Fiber Web 두께(㎛)Thickness (㎛) 2020 1One 1010 150150 250250
기공도(%)Porosity (%) 5555 5555 5555 5555 5555
회로패턴부Circuit pattern part 두께(㎛)Thickness (㎛) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
형성방법Forming method 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating
가요성 및 복원성 평가(%)Flexibility and Resilience Rating (%) 3.63.6 5.35.3 2.92.9 18.918.9 21.621.6
신축성 평가(%)Elasticity rating (%) 17.417.4 106.2106.2 42.342.3 155.3155.3 186.2186.2
내구성 평가Durability rating ○○ ×× ○○ ○○ ××
공정성 평가Fairness assessment ○○ ○○ ○○ ○○ ××
저항(Ω)Resistance (Ω) 1.211.21 58.2458.24 0.920.92 0.470.47 1.601.60
구분division 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10
나노섬유웹Nano Fiber Web 두께(㎛)Thickness (㎛) 2020 2020 2020 2020 2020
기공도(%)Porosity (%) 55 3030 6060 9090 5555
회로패턴부Circuit pattern part 두께(㎛)Thickness (㎛) 0.20.2 0.20.2 0.20.2 0.20.2 0.050.05
형성방법Forming method 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating 무전해도금Electroless Plating
가요성 및 복원성 평가(%)Flexibility and Resilience Rating (%) 21.421.4 8.88.8 3.33.3 3.23.2 2.12.1
신축성 평가(%)Elasticity rating (%) 126.2126.2 55.155.1 19.219.2 73.873.8 71.571.5
내구성 평가Durability rating ×× ○○ ○○ ×× ××
공정성 평가Fairness assessment ×× ○○ ○○ ×× ○○
저항(Ω)Resistance (Ω) 1.431.43 0.840.84 2.542.54 147.1147.1 151.7151.7
구분division 실시예11Example 11 실시예12Example 12 비교예1Comparative Example 1 비교예2Comparative Example 2
나노섬유웹Nano Fiber Web 두께(㎛)Thickness (㎛) 2020 2020 2020 2020
기공도(%)Porosity (%) 5555 5555 5555 PI기판PI substrate
회로패턴부Circuit pattern part 두께(㎛)Thickness (㎛) 33 1212 0.20.2 0.20.2
형성방법Forming method 무전해도금Electroless Plating 무전해도금Electroless Plating 포토리소그래피Photolithography 무전해도금Electroless Plating
가요성 및 복원성 평가(%)Flexibility and Resilience Rating (%) 16.616.6 31.731.7 5.15.1 3.23.2
신축성 평가(%)Elasticity rating (%) 203.5203.5 532.1532.1 18.618.6 197.1197.1
내구성 평가Durability rating ○○ ×× ×× ××
공정성 평가Fairness assessment ○○ ○○ ×× ○○
저항(Ω)Resistance (Ω) 0.520.52 0.310.31 237.3237.3 18.518.5
상기 표 1 내지 3에서 알 수 있듯이,본 발명에 따른 나노섬유웹의 두께, 기공도, 회로패턴부의 두께 및 회로패턴부 형성방법 등을 모두 만족하는 실시예 1, 3, 4, 7, 8 및 11이, 이 중에서 하나라도 누락된 실시예 2, 5, 6, 9, 10, 12 및 비교예 1 ~ 2에 비하여 가요성, 복원성, 신축성, 내구성 및 공정성이 우수한 동시에 회로로 사용할 수 있는 저항의 최소 값을 만족하되, 현저히 낮은 저항 값을 나타내었다.As can be seen from Tables 1 to 3, Examples 1, 3, 4, 7, 8 and the like satisfying all of the thickness, porosity, circuit pattern portion thickness and circuit pattern portion forming method of the nanofiber web according to the present invention and 11 has excellent flexibility, resilience, elasticity, durability, and fairness as compared to Examples 2, 5, 6, 9, 10, 12, and Comparative Examples 1 to 2, all of which are missing. The minimum value was satisfied but the resistance was significantly lower.
이상에서 본 발명의 일 실시예에 대하여 설명하였으나, 본 발명의 사상은 본 명세서에 제시되는 실시 예에 제한되지 아니하며, 본 발명의 사상을 이해하는 당업자는 동일한 사상의 범위 내에서, 구성요소의 부가, 변경, 삭제, 추가 등에 의해서 다른 실시 예를 용이하게 제안할 수 있을 것이나, 이 또한 본 발명의 사상범위 내에 든다고 할 것이다.Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiments set forth herein, and those skilled in the art who understand the spirit of the present invention, within the scope of the same idea, the addition of components Other embodiments may be easily proposed by changing, deleting, adding, and the like, but this will also fall within the spirit of the present invention.

Claims (16)

  1. (1) 섬유형성성분이 포함된 방사용액을 전기 방사하여 나노섬유웹을 제조하는 단계; 및(1) preparing a nanofiber web by electrospinning a spinning solution containing a fiber forming component; And
    (2) 무전해도금법을 통해 상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하도록 회로패턴부를 형성시키는 단계;를 포함하는 인쇄회로 나노섬유웹의 제조방법.(2) forming a circuit pattern portion to cover the outer surface of the nanofibers contained in the predetermined region on the nanofiber web by an electroless plating method.
  2. 제1항에 있어서,The method of claim 1,
    상기 나노섬유웹은 두께가 5 ~ 200㎛인 인쇄회로 나노섬유웹의 제조방법.The nanofiber web has a thickness of 5 ~ 200㎛ printed circuit nanofiber web manufacturing method.
  3. 제1항에 있어서,The method of claim 1,
    상기 나노섬유웹은 기공도가 10 ~ 80%인 인쇄회로 나노섬유웹의 제조방법.The nanofiber web has a porosity of 10 to 80% of the manufacturing method of the printed circuit nanofiber web.
  4. 제1항에 있어서,The method of claim 1,
    상기 나노섬유에 피복된 회로패턴부의 두께는 0.1 ~ 10㎛인 인쇄회로 나노섬유웹의 제조방법. The thickness of the circuit pattern portion coated on the nanofiber is 0.1 ~ 10㎛ method of manufacturing a printed circuit nanofiber web.
  5. 제1항에 있어서,The method of claim 1,
    상기 나노섬유웹은 두께가 10 ~ 150㎛ 및 기공도가 30 ~ 60%이고,The nanofiber web has a thickness of 10 to 150㎛ and porosity of 30 to 60%,
    상기 나노섬유에 피복된 회로패턴부의 두께는 0.1 ~ 3㎛인 인쇄회로 나노섬유웹의 제조방법.The thickness of the circuit pattern portion coated on the nanofibers is 0.1 ~ 3㎛ manufacturing method of the printed circuit nanofiber web.
  6. 제1항에 있어서, 상기 (2) 단계는,According to claim 1, wherein step (2),
    2-1) 상기 나노섬유웹을 촉매 용액에 침지시켜 촉매화 처리하는 단계;2-1) catalyzing the nanofiber web by immersing it in a catalyst solution;
    2-2) 촉매화 처리된 상기 나노섬유웹을 활성화시키는 단계; 및2-2) activating the catalyzed nanofiber web; And
    2-3) 활성화된 상기 나노섬유웹을 무전해도금법을 통해 회로패턴부를 형성시키는 단계;를 더 포함하는 인쇄회로 나노섬유웹의 제조방법.2-3) forming the circuit pattern portion by the electroless plating method of the activated nanofiber web; manufacturing method of a printed circuit nanofiber web further comprising.
  7. 제6항에 있어서, 상기 (2) 단계를 수행하기 전에,The method of claim 6, wherein before performing step (2),
    상기 나노섬유웹을 탈지시키거나 친수화 처리하는 단계;를 더 포함하는 인쇄회로 나노섬유웹의 제조방법.Degreasing or hydrophilizing the nanofiber web; manufacturing method of a printed circuit nanofiber web further comprising.
  8. 제6항에 있어서,The method of claim 6,
    상기 촉매 용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe의 염으로 이루어진 군에서 선택되는 어느 하나 이상의 화합물을 포함하는 인쇄회로 나노섬유웹의 제조방법.The catalyst solution is a method for producing a printed circuit nanofiber web comprising at least one compound selected from the group consisting of salts of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
  9. 제6항에 있어서, 상기 2-2) 단계는,The method of claim 6, wherein the step 2-2)
    황산용액에 침지하여 활성화시키는 단계인 인쇄회로 나노섬유웹의 제조방법.Method of manufacturing a printed circuit nanofiber web which is a step of immersing in a sulfuric acid solution to activate.
  10. 제1항에 있어서,The method of claim 1,
    상기 (2) 단계에 따른 무전해도금법은 상기 나노섬유웹 상에 회로패턴부가 형성될 부분을 제외한 나머지 면을 마스킹하여 도금용액에 침지시키는 단계인 인쇄회로 나노섬유웹의 제조방법.Electroless plating method according to the step (2) is a method of manufacturing a printed circuit nanofiber web is a step of immersing in the plating solution by masking the remaining surface except for the portion of the circuit pattern portion to be formed on the nanofiber web.
  11. 제10항에 있어서,The method of claim 10,
    상기 도금용액은 Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn 및 Fe로 이루어진 군에서 선택되는 금속을 포함하는 인쇄회로 나노섬유웹의 제조방법.The plating solution is a manufacturing method of a printed circuit nanofiber web comprising a metal selected from the group consisting of Ti, Sn, Au, Pt, Pd, Ni, Cu, Ag, Al, Zn and Fe.
  12. 제1항에 있어서, 상기 인쇄회로 나노섬유웹은The method of claim 1, wherein the printed circuit nanofiber web
    회로패턴부에 의해 형성되는 상부영역의 제1패턴과 하부영역의 제2패턴을 각각 포함하고,Each of the first pattern of the upper region and the second pattern of the lower region formed by the circuit pattern part;
    상기 제1패턴과 제2패턴은 서로 동일한 패턴으로 형성된 인쇄회로 나노섬유웹의 제조방법.The first pattern and the second pattern is a manufacturing method of a printed circuit nanofiber web formed in the same pattern.
  13. 제1항에 있어서,The method of claim 1,
    인쇄회로 나노섬유웹은 회로패턴부가 인쇄된 나노섬유웹 일면에 대향하는 면에 강도보강용 지지체를 더 구비하는 인쇄회로 나노섬유웹의 제조방법.Printed circuit nanofiber web is a method of manufacturing a printed circuit nanofiber web further comprises a strength reinforcing supporter on the surface facing the surface of the nanofiber web printed circuit pattern portion.
  14. 제1항에 있어서, The method of claim 1,
    상기 섬유형성성분은 폴리우레탄(polyurethane), 폴리스티렌(polystylene), 폴리비닐알코올(polyvinylalchol), 폴리메틸메타크릴레이트(polymethyl methacrylate), 폴리락트산(polylactic acid), 폴리에틸렌옥사이드(polyethyleneoxide), 폴리비닐아세테이트(polyvinyl acetate), 폴리아크릴산(polyacrylic acid), 폴리카프로락톤(polycaprolactone), 폴리아크릴로니트릴(polyacrylonitrile), 폴리비닐피롤리돈(polyvinylpyrrolidone), 폴리염화비닐(polyvinylchloride), 폴리카보네이트(polycarbonate), 폴리이더이미드(polyetherimide), 폴리이더술폰(polyesthersulphone), 폴리벤지미다졸(polybenzimidazol), 폴리에틸렌테레프탈레이트(polyethylene terephthalate), 폴리부틸렌테레프탈레이트(polybutylene terephthalate) 및 불소계화합물로 이루어진 군에서 선택된 1종 이상의 화합물을 포함하는 인쇄회로 나노섬유웹의 제조방법.The fiber forming component is polyurethane (polyurethane), polystyrene (polystylene), polyvinyl alcohol (polyvinylalchol), polymethyl methacrylate (polymethyl methacrylate), polylactic acid (polylactic acid), polyethylene oxide (polyethyleneoxide), polyvinylacetate ( polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyether At least one compound selected from the group consisting of polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate and fluorine-based compounds Method for producing a printed circuit nanofiber web comprising.
  15. 다수 개의 나노섬유를 포함하는 나노섬유웹; 및A nanofiber web comprising a plurality of nanofibers; And
    상기 나노섬유웹 상 소정의 영역 내에 포함된 나노섬유의 외부면을 피복하여 형성되는 회로패턴부;을 포함하는 인쇄회로 나노섬유웹.Printed circuit nanofiber web comprising a; circuit pattern portion formed by covering the outer surface of the nanofiber included in a predetermined region on the nanofiber web.
  16. 제15항에 따른 인쇄회로 나노섬유웹; 및Printed circuit nanofiber web according to claim 15; And
    상기 인쇄회로 나노섬유웹에 실장된 적어도 하나 이상의 전자 부품;을 포함하는 전자장치.And at least one electronic component mounted on the printed circuit nanofiber web.
PCT/KR2018/004600 2017-04-21 2018-04-20 Printed circuit nanofiber web manufacturing method, printed circuit nanofiber web manufactured thereby, and electronic device employing same WO2018194414A1 (en)

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